Copolymer of 1,3,7-octatriene and isoprene, hydride thereof, and method for producing said copolymer

ABSTRACT

The present invention provides a copolymer of 1,3,7-octatriene and isoprene having a narrow molecular weight distribution (Mw/Mn) and a hydride thereof. Furthermore, in a production method of a copolymer containing a structural unit derived from 1,3,7-octatriene and a structural unit derived from isoprene, high raw material conversions are achieved for a short polymerization time. Specifically, the copolymer is a copolymer containing a structural unit derived from 1,3,7-octatriene and a structural unit derived from isoprene and is a copolymer having a molecular weight distribution (Mw/Mn) of less than 1.44, or the like.

FIELD OF THE INVENTION

The present invention relates to a copolymer of 1,3,7-octatriene andisoprene and a hydride thereof, and to a method of producing thecopolymer.

BACKGROUND OF THE INVENTION

For producing films, adhesives, elastic bodies, fibers, foamed bodies,and so on, it is preferred to use a flexible, elastic, and toughpolymer, and it is known that a polymer having a glass transitiontemperature lower than a use temperature thereof (usually a roomtemperature, e.g., about 25° C.) is suitable. As the polymer having aglass transition temperature lower than room temperature, athermoplastic resin is exemplified, and as a raw material of thethermoplastic resin, butadiene which is inexpensive and easilyutilizable is frequently utilized. However, in order to improve physicalproperties of the films, adhesives, elastic bodies, fibers, foamedbodies, and so on, there is a limit because the same raw material isused, and therefore, conjugated diene compounds which are not often usedso far are interested. 1,3,7-Octatriene is one of such conjugated dienecompounds.

A polymer containing a structural unit derived from 1,3,7-octatriene hasa terminal double bond in a side chain thereof, and therefore, it can bedenatured through various reactions, for example, epoxidation,halogenation, and graft polymerization with other low-molecularcompound. In addition, maleic anhydride, acrolein, or the like can alsobe added while utilizing reactivity of the double bond existing in thepolymer. The thus-obtained chemically denatured polymer is expected tobe spread as a functional material, such as an adhesive and alubricating agent.

However, there are very few reported cases regarding polymers containinga structural unit derived from 1,3,7-octatriene. For example, there aredisclosed a polymerization method of 1,3,7-octatriene by using ananionic polymerization initiator (see PTL 1); a polymerization method of1,3,7-octatriene by using a cationic polymerization initiator (see PTL2); and a polymerization method of 1,3,7-octatriene by using atitanium-based Ziegler-type catalyst (see NPL 1). However, as for acopolymer of 1,3,7-octatriene and other conjugated diene compound, thereis disclosed only a polymerization method using a neodymium-basedZiegler-type catalyst (see NPL 2).

In NPL 2 regarding the production method of a copolymer of1,3,7-octatriene and other conjugated diene compound, as a copolymerformed from 1,3,7-octatriene and isoprene, there is disclosed acopolymer that is a copolymer in which the content of a structural unitderived from 1,3,7-octatriene is 21.0 mol % or less relative to a totalamount of the structural unit derived from 1,3,7-octatriene and astructural unit of isoprene, and when the molecular weight distribution(Mw/Mn) is narrowest as 1.44, the weight average molecular weight (Mw)is 77,760, whereas when the weight average molecular weight (Mw) islargest as 201,300, the molecular weight distribution (Mw/Mn) expands to1.83.

CITATION LIST Patent Literature

-   PTL 1: JP 49-16269 B-   PTL 2: JP 49-16268 B

Non-Patent Literature

-   NPL 1: The Journal of Organic Chemistry, Vol. 28, pp. 2699-2703    (1963)-   NPL 2: Advanced Synthesis & Catalysis, Vol. 350, pp. 431-438 (2008)

SUMMARY OF INVENTION Technical Problem

In order to enhance mechanical properties of a polymer, it is generallyknown that it is suitable to make the molecular weight distribution(Mw/Mn) narrow. In consequence, one of problems of the present inventionis to provide a copolymer of 1,3,7-octatriene and isoprene having anarrow molecular weight distribution (Mw/Mn), which has not hithertobeen produced, and a hydride thereof, and a method of producing thecopolymer.

Now, in NPL 2, it is disclosed that in the case of copolymerizing1,3,7-octatriene and isoprene in a mixing ratio of 1,3,7-octatriene of5.5 mol % relative to a total amount of 1,3,7-octatriene and isoprene inthe presence of a neodymium-based Ziegler-type catalyst, a copolymerhaving a weight average molecular weight (Mw) of 160,190 could beacquired in an isolated yield of 85% from the reaction liquid obtainedthrough polymerization at 20° C. for 20 hours. That is, there wasinvolved such a problem of difficulty in polymerization control thatwhen merely using 1,3,7-octatriene only in a ratio of 5.5 mol % incombination with isoprene, the copolymerization reaction in the presenceof a neodymium-based Ziegler-type catalyst becomes difficult to proceed,and in the case of polymerization at 20° C. for 20 hours, the isolatedyield is limited to only 85%.

In the case where the conversion of 1,3,7-octatriene is high, it becomessimple and easy to perform separation and recovery of the copolymer fromthe raw materials. Furthermore, there is no concern that unreacted1,3,7-octatriene is hydrogenated and converted into octane having aninexpensive unit price, and therefore, such is industrially preferredfrom the standpoint that an obtained copolymer can be subjected tohydrogenation reaction, etc. directly without going through a separationstep. For that reason, the matter that high raw material conversions canbe achieved for a short polymerization time is also one of problems ofthe present invention.

Solution to Problem

The present inventors made extensive and intensive investigations. As aresult, it has been found that a cause of the difficulty ofpolymerization control resides in not 1,3,7-octatriene per se butimpurities contained in 1,3,7-octatriene; and that by regulating theamount of the impurities to a predetermined value or less, thepolymerization reaction of 1,3,7-octatriene and isoprene becomes easy tobe controlled. Furthermore, it has also been noted that in the casewhere a total content of a peroxide and its decomposition product whichmay be mixed therein depending upon the production method of1,3,7-octatriene is more than a predetermined amount, it becomesdifficult to control the copolymerization of 1,3,7-octatriene andisoprene.

Then, the present inventors have found that the aforementioned problemscan be solved by using 1,3,7-octatriene having not only a purity of morethan 98.0% but also a total content of a peroxide and its decompositionproduct of 0.30 mmol/kg or less, thereby leading to accomplishment ofthe present invention.

Specifically, the present invention provides the following [1] to [26].

[1] A copolymer containing a structural unit derived from1,3,7-octatriene and a structural unit derived from isoprene, thecopolymer having a molecular weight distribution (Mw/Mn) of less than1.44.

[2] A copolymer containing a structural unit derived from1,3,7-octatriene and a structural unit derived from isoprene, thecopolymer having a molecular weight distribution (Mw/Mn) smaller than avalue determined according to the following formula (i):3.1569×10⁻⁶×[Weight average molecular weight (Mw)]+1.1945  (i).[3] A copolymer containing a structural unit derived from1,3,7-octatriene and a structural unit derived from isoprene, thecopolymer having not only the content of the structural unit derivedfrom 1,3,7-octatriene of more than 21.0 mol % relative to a total amountof the structural unit derived from 1,3,7-octatriene and the structuralunit derived from isoprene but also a molecular weight distribution(Mw/Mn) thereof of less than 2.06.[4] The copolymer as set forth in any of the above [1] to [3], having aweight average molecular weight (Mw) of 5,000 to 500,000.[5] The copolymer as set forth in any of the above [1] to [4], having aweight average molecular weight (Mw) of 20,000 to 500,000.[6] The copolymer as set forth in any of the above [1] to [5], having aweight average molecular weight (Mw) of 50,000 to 500,000.[7] The copolymer as set forth in any of the above [1] to [6], having aweight average molecular weight (Mw) of 210,000 to 500,000.[8] The copolymer as set forth in any of the above [1] to [7], nothaving a living anionic active species at a molecular end thereof.[9] The copolymer as set forth in any of the above [1] to [7], having aliving anionic active species at a molecular end thereof.[10] A copolymer containing a structural unit derived from1,3,7-octatriene and a structural unit derived from isoprene, thecopolymer having a living anionic active species at a molecular endthereof and having a molecular weight distribution (Mw/Mn) of 2.50 orless.[11] The copolymer as set forth in the above [10], having a weightaverage molecular weight (Mw) of 5,000 to 500,000.[12] The copolymer as set forth in any of the above [1] to [11], furthercontaining a structural unit derived from a conjugated diene compoundhaving 6 or more carbon atoms.[13] The copolymer as set forth in the claim [12], wherein theconjugated diene compound having 6 or more carbon atoms is at least oneselected from the group consisting of 2,3-dimethyl-1,3-butadiene,4,5-diethyl-1,3-butadiene, 2-phenyl-1,3-butadiene,2-hexyl-1,3-butadiene, 2-benzyl-1,3-butadiene, 2-p-toluyl-1,3-butadiene,2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2,3-diethyl-1,3-pentadiene, 1,3-hexadiene,2,3-dimethyl-1,3-hexadiene, 2,3-diethyl-1,3-heptadiene,3-butyl-1,3-octadiene, 2,3-dimethyl-1,3-octadiene,4,5-diethyl-1,3-octathene, 1,3-cyclohexadiene, and myrcene.[14] A hydride of the copolymer as set forth in any of the above [1] to[8] and [10] to [13].[15] A method of producing a copolymer containing a structural unitderived from 1,3,7-octatriene and a structural unit derived fromisoprene, the method including a step of subjecting 1,3,7-octatrienehaving a purity, as determined by gas chromatography, of more than 98.0%and isoprene to anionic polymerization, wherein

impurities which may be contained in the 1,3,7-octatriene include atleast one selected from the group consisting of a peroxide and itsdecomposition product, and a total content of the peroxide and itsdecomposition product in the 1,3,7-octatriene is 0.30 mmol/kg or less;and

the copolymer is satisfied with at least one of the following conditionsI to III:

Condition I: a molecular weight distribution (Mw/Mn) is less than 1.44;

Condition II: a molecular weight distribution (Mw/Mn) is smaller than avalue determined according to the following formula (i):3.1569×10⁻⁶×[Weight average molecular weight (Mw)]+1.1945  (i); and

Condition III: not only the content of the structural unit derived from1,3,7-octatriene is more than 21.0 mol % relative to a total amount ofthe structural unit derived from 1,3,7-octatriene and the structuralunit derived from isoprene, but also a molecular weight distribution(Mw/Mn) thereof is less than 2.06.

[16] The method of producing a copolymer as set forth in the above [15],wherein the 1,3,7-octatriene has a purity, as determined by gaschromatography, of 98.5% or more.

[17] The method of producing a copolymer as set forth in the above [15]or [16], wherein the anionic polymerization is carried out in thepresence of a Lewis base.

[18] The method of producing a copolymer as set forth in the above [17],wherein a molar ratio of the Lewis base to a polymerization initiatorused for the anionic polymerization [(Lewis base)/(polymerizationinitiator)] is from 0.01 to 1,000.

[19] The method of producing a copolymer as set forth in the above [17]or [18], wherein the Lewis base is a compound having at least oneselected from the group consisting of an ether bond and a tertiary aminogroup in a molecule thereof.

[20] The method of producing a copolymer as set forth in any of theabove [17] to [19], wherein the Lewis base is a compound having one atomhaving an unshared electron pair.

[21] The method of producing a copolymer as set forth in any of theabove [17] to [19], wherein the Lewis base is a compound having two ormore atoms having an unshared electron pair.

[22] The method of producing a copolymer as set forth in the above [21],wherein the Lewis base has multidentate properties.

[23] The method of producing a copolymer as set forth in any of theabove [15] to [22], wherein a solid content concentration of a reactionliquid obtained after completion of the anionic polymerization is from10 to 80% by mass.

[24] The method of producing a copolymer as set forth in any of theabove [15] to [23], wherein the anionic polymerization is carried out at−50 to 200° C.

[25] The method of producing a copolymer as set forth in any of theabove [15] to [24], wherein a conversion of the 1,3,7-octatriene aftercompletion of the anionic polymerization, as determined by gaschromatography, is 80.0% or more.

[26] The method of producing a copolymer as set forth in any of theabove [15] to [25], wherein a conversion of the 1,3,7-octatriene aftercompletion of the anionic polymerization, as determined by gaschromatography, is 88.0% or more.

Advantageous Effects of Invention

In accordance with the present invention, as for a copolymer of1,3,7-octatriene and isoprene, it is possible to provide (I) a copolymerhaving a molecular weight distribution (Mw/Mn) of less than 1.44, (II) acopolymer having a molecular weight distribution (Mw/Mn) smaller than avalue determined according to the aforementioned formula (i), and (III)a copolymer having not only the content of a structural unit derivedfrom 1,3,7-octatriene of more than 21.0 mol % relative to a total amountof a structural unit derived from 1,3,7-octatriene and a structural unitderived from isoprene but also a molecular weight distribution (Mw/Mn)thereof of less than 2.06; and a hydride of each of them.

Furthermore, in accordance with the present invention, it is possible toachieve a high conversion of each of the raw materials for a shortpolymerization time in the production of a copolymer of 1,3,7-octatrieneand isoprene.

DESCRIPTION OF EMBODIMENTS

Hereinafter, all of embodiments in which the items mentioned in thisspecification are arbitrarily combined are included in the presentinvention. In addition, a lower limit value and an upper limit value ina numerical value range may be arbitrarily combined with a lower limitvalue and an upper limit value in other numerical value range,respectively.

[Copolymer]

The present invention relates to:

(I) a copolymer containing a structural unit derived from1,3,7-octatriene and a structural unit derived from isoprene, thecopolymer having a molecular weight distribution (Mw/Mn) of less than1.44 [hereinafter sometimes referred to as “copolymer (I)”],

(II) a copolymer containing a structural unit derived from1,3,7-octatriene and a structural unit derived from isoprene, thecopolymer having a molecular weight distribution (Mw/Mn) smaller than avalue determined according to the following formula (i) [hereinaftersometimes referred to as “copolymer (II)”]:3.1569×10⁻⁶×[Weight average molecular weight (Mw)]+1.1945  (i), and

(III) a copolymer containing a structural unit derived from1,3,7-octatriene and a structural unit derived from isoprene, thecopolymer having not only the content of a structural unit derived from1,3,7-octatriene (mol %; sometimes referred to as “1,3,7-octatrienecontent α”) of more than 21.0 mol % relative to a total amount of astructural unit derived from 1,3,7-octatriene and a structural unitderived from isoprene but also a molecular weight distribution (Mw/Mn)thereof of less than 2.06 [hereinafter sometimes referred to as“copolymer (III)”].

These copolymers (I) to (III) are hereinafter sometimes referredcollectively to as “copolymer of the present invention”.

In the present invention, the weight average molecular weight (Mw) andthe number average molecular weight (Mn) are each a molecular weight asexpressed in terms of standard polystyrene as determined by means of gelpermeation chromatography (GPC) measurement, and more specifically, theyare each a value as measured by the measurement method described in thesection of Examples. In addition, the molecular weight distribution(Mw/Mn) is a value as calculated therefrom.

In the case of incorporating the copolymer of the present invention in acomposition, in order to suppress bleed-out of the copolymer, it ispreferred that not only the weight average molecular weight (Mw) of thecopolymer of the present invention is high, but also the molecularweight distribution (Mw/Mn) thereof is narrow. But, in general, when theweight average molecular weight (Mw) is made high, the molecular weightdistribution (Mw/Mn) tends to become broad. When the molecular weightdistribution (Mw/Mn) is broad, a low molecular weight material coexists,thereby possibly causing the bleed-out. On the other hand, the presentinvention is able to provide a copolymer in which the molecular weightdistribution (Mw/Mn) is kept narrow, and therefore, its industrial valueis large.

The copolymer of the present invention can be produced by using, as araw material, 1,3,7-octatriene having not only a purity of more than98.0% but also a total content of a peroxide and its decompositionproduct of 0.30 mmol/kg or less. In particular, the copolymer of thepresent invention can be produced by performing anionic polymerizationusing such a raw material. By using such a raw material, a highconversion of the raw material can be achieved for a shortpolymerization time.

The purity of 1,3,7-octatriene is preferably 98.5% or more, morepreferably 98.8% or more, and still more preferably 99.0% or more. Here,in the present invention, the purity of 1,3,7-octatriene is obtained bycalculating the sum total of peak areas capable of being assigned to thewhole of octatrienes by means of an analysis of gas chromatography anddetermining a percentage of a peak area of 1,3,7-octatriene relative tothe sum total of these peak areas, and more specifically, it is onedetermined by a method described in the section of Examples. Here, thewhole of octatrienes means all of 1,3,7-octatriene and double bondisomers thereof, such as 1,3,6-octatriene, 2,4,6-octatriene, and1,4,6-octatriene.

Examples of the impurities which may be included in 1,3,7-octatrieneinclude at least one selected from the group consisting of a peroxideand its decomposition product. A total content of the peroxide and itsdecomposition product in the 1,3,7-octatriene is preferably 0.30 mmol/kgor less, more preferably 0.15 mmol/kg or less, and still more preferably0.10 mmol/kg or less (provided that one of them may be 0 mmol/kg). Here,in the present invention, the total content of the peroxide and itsdecomposition product in the 1,3,7-octatriene is a value determined bytitrating iodine (I₂) generated by allowing potassium iodide to act on1,3,7-octatriene with sodium thiosulfate, and more specifically, it isone determined by a method described in the section of Examples.Examples of the peroxide include 5-hydroperoxy-1,3,7-octatriene and6-hydroperoxy-1,3,7-octatriene; and in addition, though thedecomposition product of a peroxide is not particularly limited so longas it is a compound capable of being produced through decomposition of5-hydroperoxy-1,3,7-octatriene or 6-hydroperoxy-1,3,7-octatriene, or thelike, examples thereof include 5-hydroxy-1,3,7-octatriene and6-hydroxy-1,3,7-octatriene. These are impurities which may be producedthrough oxygen oxidation of 1,3,7-octatriene. As the peroxide and itsdecomposition product, in particular, 5-hydroperoxy-1,3,7-octatriene,6-hydroperoxy-1,3,7-octatriene, 5-hydroxy-1,3,7-octatriene, and6-hydroxy-1,3,7-octatriene are an important compound.

As for the 1,3,7-octatriene, it is extremely difficult to performdistillation separation from a by-product, for example,4-vinylcyclohexene and 1,3,6-octatriene, and therefore, in general,1,3,7-octatriene having a purity of more than 98.0% is not easilyobtainable, and its purity is typically liable to be 97% or less. But,by carrying out the method described in JP 2016-216385 A or JP 47-17703A, it is possible to produce 1,3,7-octatriene having a purity of morethan 98.0%, and in the present invention, this 1,3,7-octatriene can beutilized. Nevertheless the 1,3,7-octatriene having a purity of more than98.0% exists like this, those skilled in the art recognized that tobegin with, the polymerization control of 1,3,7-octatriene is difficult,and therefore, they have not hitherto considered carrying out thepolymerization reaction using, as the raw material, 1,3,7-octatrienewhose purity has been especially increased to more than 98.0%. However,during the development made by the present inventors regarding thecopolymer containing a structural unit derived from 1,3,7-octatriene anda structural unit derived from isoprene, it has been found that thecopolymer of the present invention can be produced in a high conversionfor a short time by using, as the raw material, 1,3,7-octatriene havinga purity of more than 98.0%, in particular, 1,3,7-octatriene having notonly a purity of more than 98.0% but also a total content of a peroxideand its decomposition product of 0.30 mmol/kg or less.

With respect to the copolymer of the present invention, a weight averagemolecular weight (Mw) thereof is preferably 5,000 to 500,000, morepreferably 20,000 to 500,000, still more preferably 50,000 to 500,000,and especially preferably 210,000 to 500,000.

In the copolymer of the present invention, though the content of thestructural unit derived from 1,3,7-octatriene (1,3,7-octatriene contentα) relative to the total amount of the structural unit derived from1,3,7-octatriene and the structural unit derived from isoprene is notparticularly limited except for the copolymer (III), it is preferably 3to 97 mol %, more preferably 5 to 96 mol %, may be 20 to 96 mol %, maybe 20 to 70 mol %, and may be 20 to 40 mol %.

The copolymer of the present invention has only to contain a structuralunit derived from 1,3,7-octatriene and a structural unit derived fromisoprene and may further contain a structural unit derived from otherconjugated diene compound. In addition, the copolymer of the presentinvention may be a copolymer formed of only a structural unit derivedfrom 1,3,7-octatriene and a structural unit derived from isoprene. Inthe case where the copolymer of the present invention contains astructural unit derived from other conjugated diene compound, thecontent is preferably 50 mol % or less, may be 30 mol % or less, may be20 mol % or less, may be 10 mol % or less, and may be 5 mol % or lessbased on a total amount of the structural unit derived from1,3,7-octatriene, the structural unit derived from isoprene, and thestructural unit derived from other conjugated diene.

The other conjugated diene compound is preferably a conjugated dienecompound having 6 or more carbon atoms, and more preferably at least oneselected from the group consisting of 2,3-dimethyl-1,3-butadiene,4,5-diethyl-1,3-butadiene, 2-phenyl-1,3-butadiene,2-hexyl-1,3-butadiene, 2-benzyl-1,3-butadiene, 2-p-toluyl-1,3-butadiene,2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2,3-diethyl-1,3-pentadiene, 1,3-hexadiene,2,3-dimethyl-1,3-hexadiene, 2,3-diethyl-1,3-heptadiene,3-butyl-1,3-octadiene, 2,3-dimethyl-1,3-octadiene,4,5-diethyl-1,3-octadiene, 1,3-cyclohexadiene, and myrcene(7-methyl-3-methyleneocta-1,6-diene).

The copolymer of the present invention may or may not be denaturedthrough copolymerization with an anionic polymerizable compound. In thecase where the copolymer of the present invention is denatured with ananionic polymerizable compound, the content of the structural unitderived from the anionic polymerizable compound is preferably 5 mol % orless, and more preferably 3 mol % or less in the whole of structuralunits.

The anionic polymerizable compound is not particularly limited so longas it is a compound other than 1,3,7-octatriene, isoprene, and the otherconjugated diene compound and is a compound capable of undergoinganionic polymerization. Examples thereof include aromatic vinylcompounds, such as styrene, 2-chlorostyrene, 4-chlorostyrene,α-methylstyrene, α-methyl-4-methylstyrene, 2-methylstyrene,3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene,2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene,2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 4-n-propylstyrene,4-isopropylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene,4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(4-phenyl-n-butyl)styrene,1-vinylnaphthalene, 2-vinylnaphthalene, 1,1-diphenylethylene,N,N-dimethyl-p-aminoethylstyrene, N,N-diethyl-p-aminoethylstyrene,1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene,1,2-divinyl-3,4-dimethylbenzene, 2,4-divinylbiphenyl,1,3-divinylnaphthalene, 1,2,4-trivinylbenzene, 3,5,4′-trivinylbiphenyl,1,3,5-trivinylnaphthalene, and 1,5,6-trivinyl-3,7-diethylnaphthalene;α,β-unsaturated nitriles, such as acrylonitrile, methacrylonitrile, andethacrylonitrile; α,β-unsaturated carboxylic acids, such as acrylicacid, methacrylic acid, crotonic acid, 3-methylcrotonic acid, 3-butenoicacid, maleic acid, fumaric acid, itaconic acid, citraconic acid, andmesaconic acid; α,β-unsaturated carboxylic acid esters, such as methylacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, sec-butylacrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate,lauryl acrylate, stearyl acrylate, methyl methacrylate, ethylmethacrylate, propyl methacrylate, isopropyl methacrylate, butylmethacrylate, sec-butyl methacrylate, tert-butyl methacrylate, hexylmethacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearylmethacrylate, dimethyl maleate, diethyl maleate, dibutyl maleate,dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethylitaconate, diethyl itaconate, and dibutyl itaconate; and acrylamides,such as N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide,N-butylacrylamide, N-octylacrylamide, N-phenylacrylamide,N-glycidylacrylamide, N,N′-ethylenebisacrylamide,N,N-dimethylacrylamide, N-ethyl-N-methylacrylamide,N,N-diethylacrylamide, N,N-dipropylacrylamide, N,N-dioctylacrylamide,N,N-diphenylacrylamide, N-ethyl-N-glycidylacrylamide,N,N-diglycidylacrylamide, N-methyl-N-(4-glycidyloxybutyl)acrylamide,N-methyl-N-(5-glycidyloxypentyl)acrylamide,N-methyl-N-(6-glycidyloxyhexyl)acrylamide, N-acryloylpyrrolidine,N-acryloyl-L-proline methyl ester, N-acryloylpiperidine,N-acryloylmorpholine, 1-acryloylimidazole,N,N′-diethyl-N,N′-ethylenebisacrylamide,N,N′-dimethyl-N,N′-hexamethylenebisacrylamide, anddi(N,N′-ethylene)bisacrylamide.

The anionic polymerizable compounds may be used alone or may be used incombination of two or more thereof.

The copolymer of the present invention may or may not contain astructural unit derived from a coupling agent. In the case where thecopolymer of the present invention contains a structural unit derivedfrom a coupling agent, the content of the structural unit derived from acoupling agent is preferably 2.5 mol % or less, and more preferably 1.0mol % or less in the whole of structural units.

Examples of the coupling agent include dichloromethane, dibromomethane,dichloroethane, dibromoethane, dibromobenzene, and phenyl benzoate.

(Binding Mode)

In the copolymer of the present invention, as a representative bindingmode of 1,3,7-octatriene, a 1,2-bond, a 3,4-bond, a 1,4-bond, and a4,1-bond are included, and the binding order and the content ratio ofthe respective binding modes are not particularly limited. In thepresent invention, the 1,4-bond and the 4,1-bond are considered to beidentical with each other.

With respect to the binding mode of 1,3,7-octatriene, the content ratioof the 1,2-bond relative to the whole of binding modes is preferably 35to 65 mol %, more preferably 40 to 60 mol %, and still more preferably40 to 50 mol %. The content ratio of the 1,4-bond relative to the wholeof binding modes is preferably 20 to 65 mol %, more preferably 40 to 60mol %, and still more preferably 45 to 60 mol %. Taking intoconsideration the aforementioned content ratio of the 1,2-bond and theaforementioned content ratio of the 1,4-bond, the content ratio of the3,4-bond relative to the whole of binding modes becomes the remainder.Namely, the content ratio of the 3,4-bond relative to the whole ofbinding modes is determined from “100−[(content ratio of the1,2-bond)+(content ratio of the 1,4-bond)]”.

As a representative binding mode of isoprene, a 1,2-bond, a 3,4-bond,and a 1,4-bond are included, and the binding order and the content ratioof the respective binding modes are not particularly limited.

With respect to the binding mode of isoprene, the content ratio of the1,4-bond relative to the whole of binding modes is preferably 5 to 95mol %, and more preferably 10 to 90 mol %. The content ratio of the3,4-bond relative to the whole of binding modes is preferably 5 to 95mol %, and more preferably 5 to 85 mol %. Taking into consideration theaforementioned content ratio of the 1,4-bond and the aforementionedcontent ratio of the 3,4-bond, the content ratio of the 1,2-bondrelative to the whole of binding modes becomes the remainder.

Similarly, the binding mode of the other conjugated diene compound isnot particularly limited, and the binding order and the content ratio ofthe respective binding modes are not particularly limited.

The ratio of each of the binding modes is determined by the ¹³C-NMRmeasurement. Specifically, it can be determined according to the methoddescribed in the section of Examples.

(Binding Form)

In the copolymer of the present invention, a binding form between thestructural unit derived from 1,3,7-octatriene and the structural unitderived from isoprene, and in the case of further containing thestructural unit derived from the other conjugated diene compound, abinding form thereamong, are not particularly limited; however, examplesof the binding form include random, complete alternate, gradient, block,and tapered binding forms as well as combinations thereof, and a randombinding form is preferred from the viewpoint of easiness of production.

With respect to the copolymer (I), the molecular weight distribution(Mw/Mn) is preferably 1.40 or less, more preferably 1.35 or less, stillmore preferably 1.30 or less, yet still more preferably 1.20 or less,especially preferably 1.15 or less, and most preferably 1.10 or less.Though a lower limit of the molecular weight distribution (Mw/Mn) is notparticularly limited, it is typically 1.03 or more, and it often becomes1.05 or more.

With respect to the copolymer (II), the formula (i) is one determined inthe following manner. Using the weight average molecular weight (Mw) andthe molecular weight distribution (Mw/Mn) of each of Entry 4 and Entry 6in Table 1 of the aforementioned NPL 2, the weight average molecularweight (Mw) was taken on the abscissa, whereas the molecular weightdistribution (Mw/Mn) was taken on the ordinate; a formula expressing astraight line passing through two points was determined; and a formularesulting from addition of a gradient of the straight line and a valueof the intercept when the weight average molecular weight (Mw) is 0 wasdefined as the formula (i). The data of the foregoing non-patentliterature are all located on the foregoing straight line or distributedabove the straight line, and therefore, those beneath the foregoingstraight line fall within a range not disclosed in the NPL 2.

Though the range of the weight average molecular weight (Mw) in theformula (i) is not particularly limited, it is preferably 1,000 to300,000, more preferably 5,000 to 300,000, still more preferably 10,000to 300,000, especially preferably 40,000 to 300,000, and most preferably40,000 to 250,000.

With respect to the copolymer (III), the 1,3,7-octratriene content a ispreferably 40 mol % or more, more preferably 60 mol % or more, stillmore preferably 70 mol % or more, especially preferably 80 mol % ormore, and most preferably 90 mol % or more. Though an upper limit of the1,3,7-octratriene content a is not particularly limited, it may be 99mol % or less, may be 98 mol % or less, and may be 97 mol % or less.

With respect to the copolymer (III), the molecular weight distribution(Mw/Mn) is preferably 1.98 or less, more preferably 1.90 or less, stillmore preferably 1.80 or less, yet still more preferably 1.70 or less,especially preferably 1.50 or less, and most preferably 1.40 or less.Though a lower limit value of the molecular weight distribution (Mw/Mn)is not particularly limited, typically, it often becomes 1.05 or more.

On the occasion of producing the copolymer of the present inventionthrough anionic polymerization as mentioned later, the copolymer at astage after allowing a chain terminator to react after thepolymerization reaction is a copolymer not having a living anionicactive species at a molecular end thereof, and the present inventionprovides the foregoing copolymer.

On the occasion of producing the copolymer of the present inventionthrough anionic polymerization as mentioned later, the copolymer at astage before allowing a chain terminator to react after thepolymerization reaction is a copolymer having a living anionic activespecies at a molecular end thereof (sometimes referred to as “livinganionic copolymer”), and the present invention also provides theforegoing copolymer. In particular, with respect to the copolymer havinga living anionic active species at a molecular end thereof, one havingthe molecular weight distribution (Mw/Mn) of 2.50 or less can beprovided. The molecular weight distribution (Mw/Mn) is preferably 2.00or less, more preferably 1.50 or less, still more preferably 1.40 orless, and especially preferably 1.15 or less.

(Hydride)

The copolymer of the present invention may also be a hydride of theaforementioned copolymer (in general, also referred to as “hydrogenationproduct”) from the viewpoints of heat resistance and weather resistance.In the case where the copolymer of the present invention is a hydride,though a hydrogenation rate thereof is not particularly limited, in thecopolymer, the carbon-carbon double bond is hydrogenated to an extent ofpreferably 80 mol % or more, more preferably 85 mol % or more, stillmore preferably 90 mol % or more, especially preferably 93 mol % ormore, and most preferably 95 mol % or more. The foregoing value issometimes referred to as “hydrogenation rate”. Though an upper limitvalue of the hydrogenation rate is not particularly limited, it may be99 mol % or less.

The hydrogenation rate is determined by the ¹H-NMR measurement of thecontent of the carbon-carbon double bond after hydrogenation. Morespecifically, it can be determined according to the method described inthe section of Examples.

[Production Method of Copolymer]

A production method of a copolymer of the present invention is a methodof producing a copolymer (namely, the aforementioned copolymer of thepresent invention) containing a structural unit derived from1,3,7-octatriene and a structural unit derived from isoprene, the methodincluding a step of subjecting 1,3,7-octatriene having a purity, asdetermined by gas chromatography, of more than 98.0% and isoprene toanionic polymerization, wherein

impurities which may be contained in the 1,3,7-octatriene include aperoxide and its decomposition product, and a total content of theperoxide and its decomposition product in the 1,3,7-octatriene is 0.30mmol/kg or less; and

the copolymer is satisfied with at least one of the following conditionsI to III;

Condition I; a molecular weight distribution (Mw/Mn) is less than 1.44;

Condition II; a molecular weight distribution (Mw/Mn) is smaller than avalue determined according to the aforementioned formula (i); and

Condition III; not only the content of the structural unit derived from1,3,7-octatriene is more than 21.0 mol % relative to a total amount ofthe structural unit derived from 1,3,7-octatriene and the structuralunit derived from isoprene, but also a molecular weight distribution(Mw/Mn) thereof is less than 2.06.

The anionic polymerization method is not particularly limited, and aknown anionic polymerization method is applicable.

For example, an anionic polymerization initiator is fed into a mixtureof 1,3,7-octatriene and isoprene, and the aforementioned conjugateddiene compound which is optionally used (the raw materials to besubjected to polymerization reaction will be hereinafter sometimesreferred to as “raw material monomers”), to undergo polymerizationreaction, thereby forming a copolymer having a living anionic activespecies in the reaction system. Subsequently, a polymerizationterminator is added thereto, thereby producing a random copolymer.

Furthermore, a block copolymer may be produced by feeding the anionicpolymerization initiator to any one of the raw material monomers andthen adding the remaining raw material monomer or monomers to form acopolymer having a living anionic active species, followed by adding apolymerization terminator.

A Lewis base and a solvent may be used, if desired.

For the purpose of suppressing invasion of water and oxygen, etc., whichhinder the polymerization reaction, into the reaction system, forexample, it is preferred to carry out the polymerization reaction in theinterior of a reactor pressurized with an inert gas. When thepolymerization reaction is carried out in an inert gas atmosphere,consumption of the anionic polymerization initiator and a growingterminal anion by the reaction with water or oxygen can be suppressed,so that the polymerization reaction can be precisely controlled. Here,the growing terminal anion refers to an anion which the copolymerexisting in the reaction system during the polymerization reaction hasat a molecular end thereof, and hereinafter, the same is applicable.

It is preferred that 1,3,7-octatriene, isoprene, the aforementionedconjugated diene compound, an anionic polymerization initiator asmentioned later, a Lewis base as mentioned later, a solvent as mentionedlater, and so on, which are used in the production of the copolymer, donot substantially contain substances which react with the growingterminal anion to hinder the polymerization reaction, for example,oxygen, water, a hydroxy compound, a carbonyl compound, and an alkynecompound, and it is preferred that those materials are stored under ashading condition in an inert gas atmosphere of nitrogen, argon, helium,or the like.

Each of 1,3,7-octatriene, isoprene, the anionic polymerizationinitiator, the Lewis base, and so on may be used upon being diluted witha solvent or may be used without being diluted with a solvent.

As mentioned above, an important point in the production method of acopolymer of the present invention resides in the use of1,3,7-octatriene having a purity of more than 98.0% and having a totalcontent of a peroxide and its decomposition product of 0.30 mmol/kg orless (more preferably those as mentioned above).

Simultaneously, it is preferred to use compounds each having a highpurity for isoprene and the aforementioned conjugated diene compound;however, with respect to isoprene and the conjugated diene compound, itis sufficient so long as isoprene and the conjugated diene compound eachhave a purity equal to or higher than that of each of isoprene and theconjugated diene compound to be used on the occasion of the usualpolymerization thereof. In general, the purity of each of isoprene andthe conjugated diene compound as determined by gas chromatography ispreferably 99% or more. In addition thereto, it is more preferred to useisoprene and the conjugated diene compound, each of which does notsubstantially contain an alkyne, such as acetylene, an alkene, such asethylene, and a hydrocarbon compound having a functional group, such asa carbonyl group and a hydroxy group.

(Anionic Polymerization Initiator)

The production method of a copolymer of the present invention utilizesthe anionic polymerization, and therefore, an anionic polymerizationinitiator is used. The anionic polymerization initiator is not limitedin terms of its kind so long as it is able to initiate the anionicpolymerization.

As the anionic polymerization initiator, an organic alkali metalcompound which is generally used in anionic polymerization of anaromatic vinyl compound and a conjugated diene compound can be used.Examples of the organic alkali metal compound include organic lithiumcompounds, such as methyllithium, ethyllithium, propyllithium, isopropyllithium, butyllithium, sec-butyllithium, tert-butyllithium,isobutyllithium, pentyllithium, hexyllithium, butadienyllithium,cyclohexyllithium, phenyllithium, benzyllithium, p-toluyllithium,styryllithium, trimethylsilyllithium, 1,4-dilithiobutane,1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane,1,1-dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene,1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane,1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, and1,3,5-trilithio-2,4,6-triethylbenzene; and organic sodium compounds,such as methylsodium, ethylsodium, n-propylsodium, isopropylsodium,n-butylsodium, sec-butylsodium, tert-butylsodium, isobutylsodium,phenylsodium, sodium naphthalene, and cyclopentadienylsodium. Above all,n-butyllithium and sec-butyllithium are preferred. The organic alkalimetal compounds may be used alone or may be used in combination of twoor more thereof.

Though the use amount of the anionic polymerization initiator can beproperly set according to the desired weight average molecular weight ofthe living anionic polymer or solid content concentration of thereaction liquid, for example, it is preferably 10 to 3,000, morepreferably 50 to 2,500, still more preferably 100 to 2,500, andespecially preferably 300 to 2,300 in terms of a molar ratio of thetotal amount of raw material monomers to the anionic polymerizationinitiator.

(Lewis Base)

In the production method of a copolymer of the present invention, fromthe viewpoint of controlling the polymerization reaction, in particular,from the viewpoint of obtaining a high conversion of 1,3,7-octatrienefor a short time, a Lewis base may be used, and it is preferred to use aLewis base. The Lewis base is not particularly limited in terms of itskind so long as it is an organic compound which does not substantiallyreact with the anionic polymerization initiator and the growing terminalanion.

In the case of using the Lewis base, a molar ratio of the Lewis base tothe polymerization initiator (anionic polymerization initiator) to beused for the anionic polymerization [(Lewis base)/(polymerizationinitiator)] is preferably 0.01 to 1,000, more preferably 0.01 to 400,still more preferably 0.1 to 50, and especially preferably 0.1 to 20.When the foregoing molar ratio falls within this range, a highconversion of 1,3,7-octatriene is readily achieved for a short time.

As the Lewis base, there is exemplified (i) a compound having at leastone selected from the group consisting of an ether bond and a tertiaryamino group in a molecule thereof [hereinafter referred to as “Lewisbase (i)”]. Examples of the Lewis base (i) include (i-1) a compoundhaving one atom having an unshared electron pair [hereinafter referredto as “Lewis base (i-1)] and (i-2) a compound having two or more atomshaving an unshared electron pair [hereinafter referred to as “Lewis base(i-2)].

The Lewis base may be one having monodentate properties or may be onehaving multidentate properties. In addition, the Lewis base may be usedalone or may be used in combination of two or more thereof.

(Lewis Base (i))

In the Lewis base (i), specific examples of the Lewis base (i-1) includenon-cyclic monoethers, such as dimethyl ether, methyl ethyl ether,diethyl ether, ethyl propyl ether, dipropyl ether, diisopropyl ether,butyl methyl ether, tert-butyl methyl ether, dibutyl ether, dioctylether, ethyl phenyl ether, and diphenyl ether; cyclic monoethers havingpreferably 2 to 40 carbon atoms in total (more preferably 2 to 20 carbonatoms in total), such as tetrahydrofuran and tetrahydropyran; andtertiary monoamines having preferably 3 to 60 carbon atoms in total(more preferably 3 to 15 carbon atoms in total), such as trimethylamine,triethylamine, tripropylamine, triisopropylamine, tributylamine,triisobutylamine, tri-sec-butylamine, tri-tert-butylamine,tri-tert-hexylamine, tri-tert-octylamine, tri-tert-decylamine,tri-tert-dodecylamine, tri-tert-tetradecylamine,tri-tert-hexadecylamine, tri-tert-octadecylamine,tri-tert-tetracosanylamine, tri-tert-octacosanylamine,1-methyl-1-amino-cyclohexane, tripentylamine, triisopentylamine,trineopentylamine, trihexylamine, triheptylamine, trioctylamine,triphenylamine, tribenzylamine, N,N-dimethylethylamine,N,N-dimethylpropylamine, N,N-dimethylisopropylamine,N,N-dimethylbutylamine, N,N-dimethylisobutylamine,N,N-dimethyl-sec-butylamine, N,N-dimethyl-tert-butylamine,N,N-dimethylpentylamine, N,N-dimethylisopentylamine,N,N-dimethylneopentylamine, N,N-dimethylhexylamine,N,N-dimethylheptylamine, N,N-dimethyloctylamine, N,N-dimethylnonylamine,N,N-dimethyldecylamine, N,N-dimethylundecylamine,N,N-dimethyldodecylamine, N,N-dimethylphenylamine,N,N-dimethylbenzylamine, N,N-diethylmonomethylamine,N,N-dipropylmonomethylamine, N,N-diisopropylmonomethylamine,N,N-dibutylmonomethylamine, N,N-diisobutylmonomethylamine,N,N-di-sec-butylmonomethylamine, N,N-di-tert-butylmonomethylamine,N,N-dipentylmonomethylamine, N,N-diisopentylmonomethylamine,N,N-dineopentylmonomethylamine, N,N-dihexylmonomethylamine,N,N-diheptylmonomethylamine, N,N-dioctylmonomethylamine,N,N-dinonylmonomethylamine, N,N-didecylmonomethylamine,N,N-diundecylmonomethylamine, N,N-didodecylmonomethylamine,N,N-diphenylmonomethylamine, N,N-dibenzylmonomethylamine,N,N-dipropylmonomethylamine, N,N-diisopropylmonoethylamine,N,N-dibutylmonoethylamine, N,N-diisobutylmonoethylamine,N,N-di-sec-butylmonoethylamine, N,N-di-tert-butylmonoethylamine,N,N-dipentylmonoethylamine, N,N-diisopentylmonoethylamine,N,N-dineopentylmonoethylamine, N,N-dihexylmonoethylamine,N,N-diheptylmonoethylamine, N,N-dioctylmonoethylamine,N,N-dinonylmonoethylamine, N,N-didecylmonoethylamine,N,N-diundecylmonoethylamine, N,N-didodecylmonoethylamine,N,N-diphenylmonoethylamine, N,N-dibenzylmonoethylamine,N,N-dimethylaniline, N,N-diethylaniline, N-ethylpiperazine,N-methyl-N-ethylaniline, and N-methylmorpholine.

The Lewis base (i-1) is a Lewis base having monodentate properties tothe metal atom of the anionic polymerization initiator.

From the viewpoint of controlling the polymerization reaction, inparticular, from the viewpoint of obtaining a high conversion of1,3,7-octatriene for a short time, diethyl ether, diisopropyl ether,tetrahydrofuran, tetrahydropyran, triethylamine, andN,N-dimethylethylamine are preferred as the Lewis base (i-1).

In the case of using the Lewis base (i-1), a molar ratio of the atomhaving an unshared electron pair in the Lewis base (i-1) to the metalatom of the polymerization initiator used for the anionic polymerization[(atom having an unshared electron pair)/(metal atom of polymerizationinitiator)] is preferably 0.01 to 1,000, more preferably 0.1 to 500,still more preferably 2 to 300, especially preferably 2 to 100, and mostpreferably 2 to 50. When the foregoing molar ratio falls within thisrange, a high conversion of 1,3,7-octatriene is readily achieved for ashort time.

In the Lewis base (i), specific examples of the Lewis base (i-2) includenon-cyclic diethers having preferably 4 to 80 carbon atoms in total(more preferably 4 to 40 carbon atoms in total), such as1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-diisopropoxyethane,1,2-dibutoxyethane, 1,2-diphenoxyethane, 1,2-dimethoxypropane,1,2-diethoxypropane, 1,2-diphenoxypropane, 1,3-dimethoxypropane,1,3-diethoxypropane, 1,3-diisopropoxypropane, 1,3-dibutoxypropane, and1,3-diphenoxypropane; cyclic diethers having preferably 4 to 80 carbonatoms in total (more preferably to 40 carbon atoms in total), such as1,4-dioxane and 2,2-di(tetrahydrofuryl)propane; non-cyclic polyethershaving preferably 6 to 40 carbon atoms in total (more preferably 6 to 20carbon atoms in total), such as diethylene glycol dimethyl ether,dipropylene glycol dimethyl ether, dibutylene glycol dimethyl ether,diethylene glycol diethyl ether, dipropylene glycol diethyl ether,dibutylene glycol diethyl ether, triethylene glycol dimethyl ether,tripropylene glycol dimethyl ether, tributylene glycol dimethyl ether,triethylene glycol diethyl ether, tripropylene glycol diethyl ether,tributylene glycol diethyl ether, tetraethylene glycol dimethyl ether,tetrapropylene glycol dimethyl ether, tetrabutylene glycol dimethylether, tetraethylene glycol diethyl ether, tetrapropylene glycol diethylether, and tetrabutylene glycol diethyl ether; and polyamines havingpreferably 6 to 122 carbon atoms in total (more preferably 6 to 32carbon atoms in total, and still more preferably 6 to 15 carbon atoms intotal), such as N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetraethylethylenediamine,N,N,N,N″,N″-pentamethyldiethylenetriamine, andtris[2-(dimethylamino)ethyl]amine.

The Lewis base (i-2) includes a Lewis base having monodentate propertiesto the metal atom of the anionic polymerization initiator and a Lewisbase having multidentate properties to the metal atom of the anionicpolymerization initiator.

From the viewpoint of controlling the polymerization reaction, inparticular, from the viewpoint of obtaining a high conversion of1,3,7-octatriene for a short time, 1,2-dimethoxyethane,1,2-diethoxyethane, 1,2-diisopropoxyethane,2,2-di(tetrahydrofuryl)propane, N,N,N′,N′-tetramethylethylenediamine,and N,N,N′,N′-tetraethylethylenediamine are preferred as the Lewis base(i-2).

In the case of using the Lewis base (i-2), the Lewis base havingmonodentate properties to the metal atom of the anionic polymerizationinitiator and the Lewis base having multidentate properties (forexample, bidentate properties) to the metal atom of the anionicpolymerization initiator are different from each other with respect to apreferred use amount. The Lewis base (i-2) has two or more atoms havingan unshared electron pair. In this regard, when attention is paid to twoatoms having an unshared electron pair, in the case where the shortestcrosslinked carbon number connecting them is 1 (for example, —O—CH₂—O—and >N—CH₂—N<) or 3 or more (for example, —O—C₃H₆—O—, >N—C₄H₈—N<, and—O—C₃H₆—N<), each of the atoms tends to have monodentate properties. Onthe other hand, when attention is similarly paid to two atoms having anunshared electron pair, in the case where the shortest crosslinkedcarbon number connecting them is 2 (for example, —O—C₂H₄—O— and>N—C₂H₄—N<), there is a tendency that the two atoms having thoseunshared electron pairs are subjected to a multidentate arrangement(bidentate arrangement) to one metal atom of the anionic polymerizationinitiator.

In the case where the Lewis base (i-2) is a Lewis base havingmonodentate properties, a molar ratio of the atom having an unsharedelectron pair in the Lewis base (i-2) to the metal atom of thepolymerization initiator to be used for the anionic polymerization[(atom having an unshared electron pair)/(metal atom of polymerizationinitiator)] is preferably 0.01 to 1,000, more preferably 0.1 to 500,still more preferably 2 to 300, especially preferably 2 to 100, and mostpreferably 2 to 50. When the foregoing molar ratio falls within thisrange, a high conversion of 1,3,7-octatriene is readily achieved for ashort time.

On the other hand, in the case where the Lewis base (i-2) is a Lewisbase having multidentate properties (bidentate properties), a molarratio of the atom having an unshared electron pair in the Lewis base(i-2) to the metal atom of the polymerization initiator to be used forthe anionic polymerization [(atom having an unshared electronpair)/(metal atom of polymerization initiator)] is preferably 0.01 to50, more preferably 0.1 to 10, still more preferably 0.1 to 5, andespecially preferably 0.3 to 4. When the foregoing molar ratio fallswithin this range, a high conversion of 1,3,7-octatriene is readilyachieved for a short time.

In the case of a Lewis base having both monodentate properties andmultidentate properties (bidentate properties), it is preferred todetermine the use amount of the Lewis base by combing an atom havingunshared electron pair having monodentate properties with two or moreatoms having unshared electron pair having multidentate properties(bidentate properties), paying attention thereto, and referring to theaforementioned description.

(Solvent)

Though the production method of a copolymer of the present invention canbe carried out in the absence of a solvent, for the purpose ofefficiently removing polymerization heat, it is preferred to carry outthe production in the presence of a solvent.

Though the solvent is not particularly limited in terms of its kind solong as it does not substantially react with the anionic polymerizationinitiator and the growing terminal anion, a hydrocarbon-based solvent ispreferred from the viewpoint of precisely controlling the polymerizationtime and the conversion with the Lewis base.

Examples of the hydrocarbon-based solvent include saturated aliphatichydrocarbons, such as isopentane (27.9° C.; a boiling point at 1 atm,hereinafter the same), pentane (36.1° C.), cyclopentane (49.3° C.),hexane (68.7° C.), cyclohexane (80.7° C.), heptane (98.4° C.),isoheptane (90° C.), isooctane (99° C.), 2,2,4-trimethylpentane (99°C.), methylcyclohexane (101.1° C.), cycloheptane (118.1° C.), octane(125.7° C.), ethylcyclohexane (132° C.), methylcycloheptane (135.8° C.),nonane (150.8° C.), and decane (174.1° C.); and aromatic hydrocarbons,such as benzene (80.1° C.), toluene (110.6° C.), ethylbenzene (136.2°C.), p-xylene (138.4° C.), m-xylene (139.1° C.), o-xylene (144.4° C.),propylbenzene (159.2° C.), and butylbenzene (183.4° C.).

When a solvent having a boiling point of lower than that of1,3,7-octatriene (boiling point: 125.5° C.) that is one of the rawmaterial monomers is used, the polymerization heat can be efficientlyremoved by means of reflux condensation cooling of the solvent, andhence, such is preferred. From this viewpoint, isopentane (27.9° C.),pentane (36.1° C.), cyclopentane (49.3° C.), hexane (68.7° C.),cyclohexane (80.7° C.), heptane (98.4° C.), isoheptane (90° C.),isooctane (99° C.), 2,2,4-trimethylpentane (99° C.), methylcyclohexane(101.1° C.), cycloheptane (118.1° C.), benzene (80.1° C.), and toluene(110.6° C.) are preferred. Above all, from the same viewpoint,cyclohexane and n-hexane are more preferred.

The solvents may be used alone or may be used in combination of two ormore thereof.

Though the use amount of the solvent is not particularly limited, it isregulated such that a solid content concentration of the reaction liquidobtained after completion of the anionic polymerization is preferably 10to 80% by mass, more preferably 10 to 70% by mass, still more preferably15 to 65% by mass, especially preferably 15 to 55% by mass, and mostpreferably 25 to 55% by mass. In addition, it is preferred to regulatethe use amount of the solvent such that a concentration of the livinganionic polymer in the reaction system is 5% by mass or more, and it ismore preferred to regulate the use amount of the solvent such that theconcentration of the living anionic polymer is 10 to 80% by mass. Whenthe solvent is used in such an amount, the removal of polymerizationheat can be achieved at a level suited for industrial production, andtherefore, not only the polymerization time is readily shortened, butalso a high conversion of 1,3,7-octatriene is readily achieved.Furthermore, when the solvent is used in such an amount, the molecularweight distribution is readily made narrow.

From the viewpoint of making the step of removing the solvent simple,the concentration of the solid content in the reaction liquid aftercompletion of anionic polymerization may be adjusted to 35 to 80% bymass, and may be adjusted to 50 to 70% by mass.

(Reactor)

A type of a reactor is not particularly limited, a complete mixing typereactor, a tubular reactor, and a reaction apparatus in which two ormore of these reactors are connected in series or in parallel can beused. From the viewpoint of producing a copolymer having a narrowmolecular weight distribution (Mw/Mn) at a high solution viscosity, itis suitable to use a complete mixing type reactor. Though an impeller ofthe reactor is not particularly limited, examples thereof include a maxblend blade, a full-zone blade, a paddle blade, a propeller blade, aturbine blade, a fan turbine blade, a Pfaudler blade, and a blue marginblade, and a combination of any two or more thereof may also be used. Inthe case where the viscosity of the obtained polymer solution is high,from the viewpoints of making the molecular weight distribution (Mw/Mn)narrow and promoting the jacket heat removal, it is preferred to use amax blend blade or a full-zone blade.

An agitation method may be either upper portion agitation or lowerportion agitation.

A polymerization method is not particularly limited, and it may becarried out by all of batch, semi-batch, and continuous systems. For thepurpose of heating and cooling of the solution in the inside of thereactor, the complete mixing type reactor may be provided with a jacketin the outside thereof, and a structure thereof is not particularlylimited, and a known system can be adopted. In addition, for the purposeof increasing cooling heat transfer, if desired, a cooling baffle or acooling coil, etc. may be attached to the inside of the reactor.Furthermore, a direct or indirect type reflux condenser may be attachedto a gas phase portion. From the viewpoint of controlling the removalamount of polymerization heat, the reactor may be pressurized with aninert gas, or may be evacuated to atmospheric pressure or lower. In thecase of reducing the internal pressure of the reactor to atmosphericpressure or lower, a pump for venting the inert gas may be installed viathe reflux condenser. Though a structure of the reflux condenser is notparticularly limited, it is preferred to use a multitubular refluxcondenser. As for the reflux condenser, plural reflux condensers may beconnected in series or in parallel, and a different coolant may be madeto pass through each of the reflux condensers. A temperature of thecolorant which is made to pass through the reflux condenser is notparticularly limited within a range of from a temperature at which thesolvent to be refluxed is not frozen to the reaction liquid temperature;however, so long as it is preferably −20 to 50° C., and more preferably5 to 30° C., a large-sized refrigerating machine is not needed, andhence, such is economical.

(Polymerization Temperature)

Though the polymerization temperature is not particularly limited, it ispreferred to carry out the polymerization within a range of from atemperature equal to or higher than the freezing points of the chemicalsto a temperature equal to or lower than the temperatures at which thechemicals are not heat-decomposed. So long as the polymerizationtemperature is preferably −50 to 200° C., more preferably −20 to 120°C., and still more preferably 15 to 100° C., a copolymer havingexcellent mechanical properties, which is capable of suppressingproduction of a low-molecular weight polymer to be caused due to partialthermal degradation of the growing terminal anion, can be produced whileshortening the polymerization time and keeping the high conversion of1,3,7-octatriene.

(Polymerization Pressure)

The polymerization of the present invention can be suitably carried outso long as incorporation of a substance which reacts with the growingterminal anion to hinder the polymerization reaction, for example, theair containing oxygen and water, is suppressed.

In the case of using a solvent having a boiling point equal to or lowerthan the polymerization temperature, the temperature may be controlledby controlling the pressure with an inert gas to control the generationamount of a solvent vapor, or in the case of using a solvent having aboiling point higher than the polymerization temperature, thetemperature may be controlled by reducing the pressure in the reactionsystem by using a vacuum pump to control the generation amount of avapor of the solvent.

Though the polymerization pressure is not particularly limited, so longas it is 0.01 to 10 MPaG, and more preferably 0.1 to 1 MPaG, not onlythe use amount of the inert gas is reduced, but also a highpressure-resistant reactor and a pump of venting the inert gas outsidethe system become unnecessary, and hence, the polymerization can beperformed economically advantageously.

(Polymerization Time)

Though the polymerization time is not particularly limited, so long asit is preferably 0.1 to 24 hours, and more preferably 0.5 to 12 hours, apolymer having excellent mechanical properties, which is capable ofsuppressing production of a low-molecular weight polymer to be causeddue to partial thermal degradation of the growing terminal anion, isreadily produced.

(Polymerization Terminator and Coupling Agent)

In the production method of a copolymer of the present invention, it ispreferred to add a polymerization terminator to the reaction system,thereby terminating the polymerization reaction. Examples of thepolymerization terminator include a hydrogen molecule; an oxygenmolecule; water; alcohols, such as methanol, ethanol, propanol,isopropanol, butanol, heptanol, cyclohexanol, phenol, benzyl alcohol,o-cresol, m-cresol, p-cresol, ethylene glycol, propylene glycol,butanediol, glycerin, and catechol; halides, such as methyl chloride,methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyliodide, butyl chloride, butyl bromide, butyl iodide, benzyl chloride,benzyl bromide, benzyl iodide, trimethylsilyl fluoride, trimethylsilylchloride, trimethylsilyl bromide, trimethylsilyl iodide, triethylsilylfluoride, triethylsilyl chloride, triethylsilyl bromide, triethylsilyliodide, tributylsilyl fluoride, tributylsilyl chloride, tributylsilylbromide, tributylsilyl iodide, triphenylsilyl fluoride, triphenylsilylchloride, triphenylsilyl bromide, and triphenylsilyl iodide; ketones,such as 2-heptanone, 4-methyl-2-pentanone, cyclopentanone, 2-hexanone,2-pentanone, cyclohexanone, 3-pentanone, acetophenone, 2-butanone, andacetone; esters, such as methyl acetate, ethyl acetate, and butylacetate; epoxy compounds, such as ethylene oxide, propylene oxide,1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and cyclohexaneoxide; and silyl hydride compounds, such as methyldichlorosilane,ethyldichlorosilane, propyldichlorosilane, butyldichlorosilane,pentyldichlorosilane, hexyldichlorosilane, heptyldichlorosilane,octyldichlorosilane, nonyldichlorosilane, decyldichlorosilane,phenyldichlorosilane, dimethylchlorosilane, diethylchlorosilane,dipropylchlorosilane, dibutylchlorosilane, dipentylchlorosilane,dihexylchlorosilane, diheptylchlorosilane, dioctylchlorosilane,dinonylchlorosilane, didecylchlorosilane, methylpropylchlorosilane,methylhexylchlorosilane, methylphenylchlorosilane, diphenylchlorosilane,dimethylmethoxysilane, dimethylethoxysilane, dimethylpropoxysilane,dimethylbutoxysilane, dimethylphenoxysilane, dimethylbenzyloxysilane,diethylmethoxysilane, diethylethoxysilane, diethylpropoxysilane,diethylbutoxysilane, diethylphenoxysilane, diethylbenzyloxysilane,dipropylmethoxysilane, dipropylethoxysilane, dipropylpropoxysilane,dipropylbutoxysilane, dipropylphenoxysilane, dipropylbenzyloxysilane,dibutylmethoxysilane, dibutylethoxysilane, dibutylpropoxysilane,dibutylbutoxysilane, dibutylphenoxysilane, dibutylbenzyloxysilane,diphenylmethoxysilane, diphenylethoxysilane, diphenylpropoxysilane,diphenylbutoxysilane, diphenylphenoxysilane, diphenylbenzyloxysilane,dimethylsilane, diethylsilane, dipropylsilane, dibutylsilane,diphenylsilane, diphenylmethylsilane, diphenylethylsilane,diphenylpropylsilane, diphenylbutylsilane, trimethylsilane,triethylsilane, tripropylsilane, tributylsilane, triphenylsilane,methylsilane, ethylsilane, propylsilane, butylsilane, phenylsilane,methyldiacetoxysilane, polymethylhydrosiloxane, polyethylhydrosiloxane,polypropylhydrosiloxane, polybutylhydrosiloxane,polypentylhydrosiloxane, polyhexylhydrosiloxane,polyheptylhydrosiloxane, polyoctylhydrosiloxane, polynonylhydrosiloxane,polydecylhydrosiloxane, polyphenylhydrosiloxane,1,1,3,3-tetramethyldisiloxane, methylhydrocyclosiloxane,ethylhydrocyclosiloxane, propylhydrocyclosiloxane,butylhydrocyclosiloxane, phenylhydrocyclosiloxane,1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetraethyldisilazane,1,1,3,3-tetrapropyldisilazane, 1,1,3,3-tetrabutyldisilazane, and1,1,3,3-tetraphenyldisilazane.

The polymerization terminators may be used alone or may be used incombination of two or more thereof.

The polymerization terminator may be used upon being diluted with asolvent which can be used for the polymerization reaction. Though theuse amount of the polymerization terminator is not particularly limited,the matter that the use amount of the polymerization terminator does notbecome excessive relative to the growing terminal anion is preferredfrom the viewpoint of recovering and reusing the solvent, and in thecase of hydrogenating the copolymer, such is also preferred from thestandpoint that the use amount of a hydrogenation catalyst can bereduced.

A conversion of the 1,3,7-octatriene after completion of the anionicpolymerization, as determined by gas chromatography, is preferably 80.0%or more, more preferably 88.0% or more, more preferably 90.0% or more,still more preferably 95.0% or more, especially preferably 97.0% ormore, and most preferably 98.0% or more, and it is also possible toachieve the conversion of 99.0% or more.

(Hydrogenation Reaction)

From the viewpoints of heat resistance, oxidation resistance, weatherresistance, ozone resistance, etc. of the copolymer, at least a part orthe whole of carbon-carbon double bonds which the copolymer has may behydrogenated. Typically, in the production method of the copolymer, tothe polymer solution obtained by polymerization termination or thepolymer solution optionally diluted with the aforementioned solvent, ahydrogenation catalyst is added to act on hydrogen, a hydride of thecopolymer can be produced.

Examples of the hydrogenation catalyst include Raney nickel; aheterogeneous catalyst in which a metal, such as Pt, Pd, Ru, Rh, and Ni,is supported on a carrier, such as carbon, alumina, and diatomaceousearth; a Ziegler-type catalyst composed of a combination of a transitionmetal compound with an alkylaluminum compound, an alkyllithium compound,or the like; and a metallocene-based catalyst.

A temperature of the hydrogenation reaction is preferably −20 to 250°C., the temperature of which is equal to or higher than the freezingpoint of the solvent and not higher than the heat decompositiontemperature of the copolymer, and it is more preferably 30 to 150° C.from the viewpoint of industrially advantageously producing the hydrideof the copolymer. When the hydrogenation reaction temperature is 30° C.or higher, the hydrogenation reaction is advanced, and when it is 150°C. or lower, even if heat decomposition of the hydrogenation catalystoccurs, the hydrogenation reaction can be carried out at a low useamount of the hydrogenation catalyst. The hydrogenation reactiontemperature is still more preferably 60 to 100° C. from the viewpoint ofreducing the use amount of the hydrogenation catalyst.

The hydrogen can be used in a gaseous form, and its pressure is notparticularly limited so long as it is atmospheric pressure or higher;however, it is preferably 0.1 to 20 MPaG from the viewpoint ofindustrially advantageously producing a hydride of the copolymer. Whenthe pressure is 20 MPaG or lower, even if hydrogen decomposition of thehydrogenation catalyst occurs, the hydrogenation reaction can be carriedout at a low use amount of the hydrogenation catalyst. The pressure ofhydrogen is still more preferably 0.5 to 10 MPaG from the viewpoint ofreducing the use amount of the hydrogenation catalyst.

Though the time required for the hydrogenation reaction can be properlyselected according to a condition, it is preferably a range of from 10minutes to 24 hours since commencement of co-presence of the catalystfrom the viewpoint of industrially advantageously producing a hydride ofthe copolymer.

As for the reaction mixed liquid after completion of the hydrogenationreaction, after being optionally diluted with the aforementioned solventor concentrated, it is washed with a basic aqueous solution or an acidicaqueous solution, whereby the hydrogenation catalyst can be removed.

As for the polymer solution obtained after the polymerization reactionor the polymer solution obtained after the hydrogenation reaction, aftersubjecting to a concentration operation, the resultant may be fed intoan extruder, thereby isolating the copolymer; it may be brought intocontact with steam to remove the solvent and so on, thereby isolatingthe copolymer; or it may be brought into contact with an inert gas in aheated state to remove the solvent and so on, thereby isolating thecopolymer.

(Production Method of High-Purity 1,3,7-Octatriene)

As the production method of 1,3,7-octatriene, a production method of1,3,7-octatriene having a purity, as determined by gas chromatography,of more than 98.0% is selected; or in the case of 1,3,7-octatrienehaving a purity of 98.0% or less, it is necessary to purity it toacquire 1,3,7-octatriene having a purity of more than 98.0%.

For example, a method of dimerizing butadiene in the presence of apalladium catalyst, as described in JP 46-24003 B; and deacetylationreaction of 1-acetoxy-2,7-octadiene as described in JP 47-17703 A can beutilized.

On the occasion of producing 1,3,7-octatriene, it is known that1,3,6-octatriene, 2,4,6-octatriene, or the like, in which the positionof a double bond is different, is formed as a by-product. Owing to thematter that a boiling point of such a by-product is close to the boilingpoint of 1,3,7-octatriene, it is difficult to undergo distillationseparation of the by-product from 1,3,7-octatriene, and therefore, it ispreferred to adopt the production method of 1,3,7-octatriene, in whichthe by-product is a few.

In the case where the total content of a peroxide and its decompositionproduct in 1,3,7-octatriene is more than 0.30 mmol/kg, it is necessaryto use 1,3,7-octatriene after reducing the contents of the peroxide andits decomposition product. Though a method of reducing the contents ofthe peroxide and its decomposition product is not particularly limited,examples thereof include an alumina treatment; and a method in which acompound having a function as an antioxidant and having a higher boilingpoint than that of 1,3,7-octatriene (for example, 4-tert-butyl catechol,2,4-di-tert-butylphenol, and triphenyl phosphine) is mixed with1,3,7-octatriene, followed by performing a distillation treatment. Aboveall, it is preferred to utilize an alumina treatment.

EXAMPLES

The present invention is hereunder described in more detail by referenceto Examples, but it should be construed that the present invention is byno means limited by such Examples.

The production of 1,3,7-octatriene was carried out in an inert gasatmosphere of nitrogen, argon, or the like, without being particularlyindicated.

As for all of liquid medicines, those obtained by not only substitutinga dissolved gas with an inert gas but also removing an antioxidant andwater were used unless otherwise indicated.

As 2,7-octadien-1-ol that is a production raw material of1,3,7-octatriene, 2,7-octadien-1-ol having a purity of 99.54%, asmanufactured by Kuraray Co., Ltd., was used. The foregoing purity wasdetermined according to the following measurement method.

(Measurement Method of Purity of 2,7-Octadien-1-ol)

The purity of 2,7-octadien-1-ol was determined by means of an analysisof gas chromatography under the following measurement condition.Specifically, a percentage of a “peak area capable of assigning to one2,7-octadien-1-ol capable of being observed for a retention time ofabout 17.6 minutes” relative to “sum total of peak areas detected for aretention time of 5 to 20 minutes” was determined, and this was definedas the purity of 2,7-octadien-1-ol. The purity of 2,7-octadien-1-ol wasfound to be 99.54%.

<Measurement Condition of Gas Chromatography>

Apparatus: “GC-2010 Plus”, manufactured by Shimadzu Corporation

Column: “Rxi-5 ms” (inside diameter: 0.25 mm, length: 30 m, filmthickness: 1 μm), manufactured by Restek Corporation

Carrier gas: Helium (113.7 kPaG) was allowed to flow at a flow rate of1.37 mL/min.

Injection amount of sample: 0.1 μL of the liquid medicine was injectedat a split ratio of 100/1.

Detector: FID

Temperature of detector: 280° C.

Temperature of vaporization chamber: 280° C.

Temperature rise condition: After holding at 70° C. for 12 minutes, thetemperature was raised to 280° C. at a rate of 20° C./min, followed byholding for 5 minutes.

Production Example 1 Production of 1,3,7-Octatriene

(Acetylation Reaction of 2,7-Octadiene-1-ol)

A flask having a capacity of 10 L and equipped with a thermometer, anitrogen feed inlet, a dropping funnel having a capacity of 2 L, and astirrer was prepared. After purging the interior of the flask withnitrogen, 1,500.8 g (11.892 mol) of 2,7-octadien-1-ol, 1,806.3 g (17.851mol) of triethylamine, and 72.60 g (0.594 mol) of4-dimethylaminopyridine were successively charged, and then, thecontents were cooled by using a dry ice-acetone bath while stirring at140 rpm until the liquid temperature reached −40° C., thereby obtaininga mixed liquid. Meanwhile, 1,821.5 g (17.842 mol) of acetic anhydridewas charged in the dropping funnel, and the acetic anhydride was addeddropwise over 1 hour such that the liquid temperature of theaforementioned mixed liquid was kept at −50 to −30° C.

After completion of the dropwise addition, the reaction was continuedfor 1 hour, and 700.0 g of distilled water was added to terminate thereaction. The organic phase was recovered and then successively washedwith 1 L of a 5% hydrochloric acid two times, 1 L of a saturated sodiumhydrogencarbonate aqueous solution two times, 1 L of distilled water onetime, and 1 L of a saturated sodium chloride aqueous solution one time.The thus obtained organic phase was dehydrated by the addition of 170 gof anhydrous sodium sulfate, and the anhydrous sodium sulfate was thenfiltered off, to recover the organic phase.

The recovered organic phase was analyzed by means of gas chromatographyunder the same condition as in the aforementioned purity analysis of2,7-octadien-1-ol, to calculate a purity of 1-acetoxy-2,7-octadiene. Apercentage of a “sum total of two peak areas capable of being observedfor a retention time of about 19.2 minutes and about 19.3 minutes,respectively” relative to a “sum total of peak areas detected for aretention time of 5 to 20 minutes”, namely the purity of1-acetoxy-2,7-octadiene was found to be 99.51%. 1,851.1 g (yield: 92.5%)of 1-acetoxy-2,7-octadiene having the foregoing purity was acquired.

(Deacetylation Reaction of 1-Acetoxy-2,7-Octadiene)

An interior of a 3-L vacuum distillation apparatus equipped with aClaisen tube distillation head connected with a receiver via a Liebigcondenser, a stirrer, and a thermometer was purged with nitrogen, and1,205.7 g (7.167 mol) of the above-obtained 1-acetoxy-2,7-octadiene,26.7 g (0.119 mol) of palladium acetate, and 124.8 g (0.4758 mol) oftriphenyl phosphine were charged. An internal pressure was controlled to1.52 to 1.35 kPaA with a vacuum controller while stirring at 200 rpm,and distillation was performed at a rate of 8.0 g/min while heating suchthat the liquid temperature was 90° C. After removing 41.4 g of aninitial distillate, 799.7 g of a subsequently distillated product wasrecovered.

The recovered distillate was successively washed with 500 mL of a 0.2mol/L sodium hydroxide aqueous solution three times, 500 mL of distilledwater one time, and 500 mL of a saturated sodium chloride aqueoussolution one time. The organic phase was dried by the addition of 50 gof anhydrous sodium sulfate, and the anhydrous sodium sulfate was thenfiltered off, to recover the organic phase.

The recovered organic phase was analyzed by means of gas chromatographyunder the same condition as in the aforementioned purity analysis of2,7-octadien-1-ol, and as a result, it was found to be a mixturecomposed of 46.9% of 1,3,7-octatriene, 23.7% of 1-acetoxy-2,7-octadiene,and 29.4% of 3-acetoxy-1,7-octadiene. 637.0 g of the organic phase wascharged in a distillation apparatus having a McMahon packing filledtherein and having an inside diameter of 25.4 mm and a height of 240 mm.A distillate was recovered under a condition at 22.1 to 13.0 kPaA suchthat a reflux ratio was 2 at 79.1 to 60.3° C.

The recovered organic phase was analyzed by means of gas chromatographyunder the same condition as in the aforementioned purity analysis of2,7-octadien-1-ol, to calculate a purity of 1,3,7-octatriene. Apercentage of a “sum of two peak areas capable of being assigned to1,3,7-octatriene and observed for a retention time of near 8.7 minutesand 9.0 minutes, respectively” relative to a “sum total of peak areascapable of being assigned to all of the octatrienes and detected for aretention time of 5 to 20 minutes” was calculated according to thefollowing formula 1, and as a result, it was found to be 99.3%. Here,all of the octatrienes mean all of 1,3,7-octatriene and double-bondisomers, such as 1,3,6-octatriene, 2,4,6-octatriene, and1,4,6-octatriene.

$\begin{matrix}{{{Purity}\mspace{14mu}(\%)} = {\frac{{Peak}\mspace{14mu}{area}\mspace{14mu}{of}\mspace{14mu} 1,3,7\text{-}{octatriene}}{{{Sum}\mspace{14mu}{total}\mspace{14mu}{of}\mspace{14mu}{peak}\mspace{14mu}{areas}}\mspace{25mu}{{of}\mspace{14mu}{all}\mspace{14mu}{of}\mspace{14mu}{octatrienes}}} \times 100}} & \left( {{Formula}\mspace{14mu} 1} \right)\end{matrix}$

A total content of the peroxide and its decomposition product in theabove-obtained 1,3,7-octatriene was measured according to the followingmeasurement method.

(Measurement Method of Total Content of Peroxide and its DecompositionProduct)

After purging a 100-mL three-necked flask equipped with a gas feed portand a condenser with nitrogen, 5.00 g of 1,3,7-octatriene obtained bythe aforementioned method was precisely weighed, 20.0 g of isopropylalcohol, 5.0 g of distilled water, 2.0 g of acetic acid, and 1.6 g ofpotassium iodide dissolved in 1.5 g of distilled water were added, andthen, the contents were heated and stirred for 5 minutes by using an oilbath at 95° C.

After taking out the three-necked flask from the oil bath, the interiorof the condenser was washed with a mixed solvent of 6.0 g of isopropylalcohol and 1.5 g of distilled water, and the washing liquid was mixedwith the solution in the three-necked flask. After allowing to stand forcooling to room temperature, 0.005 mmol/mL of a sodium thiosulfateaqueous solution was added dropwise to the three-necked flask, and thetotal content of a peroxide and its decomposition product was calculatedfrom a volume at which the color was faded from yellow to colorlessaccording to the following formula 2. As a result, the total content ofthe peroxide and its decomposition product in 1,3,7-octatriene was foundto be less than 0.015 mmol/kg.

$\begin{matrix}{{{Total}\mspace{14mu}{content}\mspace{14mu}{of}\mspace{14mu}{perocide}\mspace{14mu}{and}}\;\mspace{124mu}{{{its}\mspace{14mu}{decomposition}\mspace{14mu}{product}\mspace{14mu}\left( {{mmol}\text{/}{kg}} \right)} = \frac{\;\begin{matrix}{0.005\mspace{14mu}\left( {{mmol}\text{/}{mL}} \right) \times \left\lbrack {{Dropwise}\mspace{14mu}{addition}}\mspace{11mu} \right.} \\\left. {{amount}\mspace{14mu}{of}\mspace{14mu}{sodium}\mspace{14mu}{thiosulfate}\mspace{14mu}({mL})} \right\rbrack\end{matrix}}{2 \times 0.005\mspace{14mu}({kg})}}} & \left( {{Formula}\mspace{14mu} 2} \right)\end{matrix}$

There was thus obtained 1,3,7-octatriene having a purity of 99.3% andhaving a total content of the peroxide and its decomposition product ofless than 0.015 mmol/kg. The results are shown in Table 1.

Production Example 2 Production of 1,3,7-Octatriene

The 1,3,7-octatriene acquired in Production Example 1 was transferredinto a glass flask and allowed to stand at room temperature (20 to 25°C.) for 100 hours in an air atmosphere without shading. The purity ofthe obtained 1,3,7-octatriene and the total content of the peroxide andits decomposition product are shown in Table 1.

Production Example 3 Production of 1,3,7-Octatriene

The 1,3,7-octatriene acquired in Production Example 1 was transferredinto a glass flask and allowed to stand at room temperature (20 to 25°C.) for 200 hours in an air atmosphere without shading. The purity ofthe obtained 1,3,7-octatriene and the total content of the peroxide andits decomposition product are shown in Table 1.

Production Example 4 Production of 1,3,7-Octatriene (for ComparativeExample 1)

The same operations as in Production Example 1 were followed, exceptthat the distillation rate of 1,3,7-octatriene from the reaction systemwas changed to 5.0 g/min such that the purity of 1,3,7-octatriene wasone as shown in Table 1. The acquired 1,3,7-octatriene was transferredinto a glass flask and allowed to stand at room temperature (20 to 25°C.) for 90 hours in an air atmosphere without shading. The purity of theobtained 1,3,7-octatriene and the total content of the peroxide and itsdecomposition product are shown in Table 1.

Production Example 5 Production of 1,3,7-Octatriene (for ReferenceExample 1)

The same operations as in Production Example 1 were followed, exceptthat the distillation rate of 1,3,7-octatriene from the reaction systemwas changed to 4.0 g/min such that the purity of 1,3,7-octatriene wasone as shown in Table 1. The acquired 1,3,7-octatriene was transferredinto a glass flask and allowed to stand at room temperature (20 to 25°C.) for 120 hours in an air atmosphere without shading. The purity ofthe obtained 1,3,7-octatriene and the total content of the peroxide andits decomposition product are shown in Table 1.

Production Example 6 Production of 1,3,7-Octatriene (for ReferenceExample 2)

The 1,3,7-octatriene acquired in Production Example 1 was transferredinto a glass flask and put into cold storage for 2,000 hours in an airatmosphere. The purity of the obtained 1,3,7-octatriene and the totalcontent of the peroxide and its decomposition product are shown in Table1.

TABLE 1 Production Example 1,3,7-Octatriene 1 2 3 4 5 6 Purity (%) 99.399.2 99.2 97.98 96.72 99.2 Total content of <0.015 0.065 0.26 0.0620.073 3.37 peroxide and its decomposition product (mmol/kg)

Hereinafter, the production of a copolymer was carried out in an argongas atmosphere unless otherwise indicated.

As reagents used in each of the Examples, the following were used.

As for isoprene, isoprene (containing a stabilizer), manufactured byWako Pure Chemical Industries, Ltd., from which moisture and thestabilizer had been removed by using Molecular Sieves 3A and neutralactive alumina and further subjected to bubbling with an argon gas topurge the dissolved gas, was used.

As for cyclohexane, cyclohexane (not containing a stabilizer),manufactured by Wako Pure Chemical Industries, Ltd., from which moisturehad been removed by using Molecular Sieves 3A and further subjected tobubbling with an argon gas to purge the dissolved gas, was used.

As for sec-butyllithium, a cyclohexane solution of sec-butyllithium,manufactured by Asia Lithium Corporation, a concentration of which hadbeen adjusted with the aforementioned cyclohexane to 1.26 mmol/g, wasused.

All of tetrahydrofuran (not containing a stabilizer), diethyl ether(containing a stabilizer), triethylamine, 1,2-diethoxyethane (DEE), andN,N,N′,N′-tetramethylethylenediamine (TMEDA), all of which aremanufactured by Wako Pure Chemical Industries, Ltd., and2,2-di(2-tetrahydrofuryl)propane (DTHFP), manufactured by Tokyo ChemicalIndustry Co., Ltd., from which moisture and the stabilizer had beenremoved by using neutral active alumina and further subjected tobubbling with an argon gas to purge the dissolved gas, were used.

As for polystyrene, standard polystyrene (weight average molecularweight (Mw)=1,300, molecular weight distribution (Mw/Mn)=1.06),manufactured by Wako Pure Chemical Industries, Ltd. was used.

In each of the following Examples, with respect to the conversion ofeach of 1,3,7-octatriene and isoprene, the yield, weight averagemolecular weight (Mw), and molecular weight distribution (Mw/Mn) of thecopolymer, and the binding mode were determined according to thefollowing measurement methods, respectively.

(Measurement Method of Conversion)

1.00 g of ethylene glycol dimethyl ether was added to 5.00 g of thepolymerization-terminated liquid after completion of the polymerizationreaction, and this mixed liquid was analyzed by means of gaschromatography under the following measurement condition.

The conversion (%) of 1,3,7-octatriene was calculated from a “relativearea ratio of 1,3,7-octatriene and ethylene glycol dimethyl ether at 0hour of commencement of polymerization reaction” and a “relative arearatio of unreacted 1,3,7-octatriene and ethylene glycol dimethyl etherafter completion of polymerization reaction” according to the followingformula 3.

The conversion (%) of isoprene was calculated from a “relative arearatio of isoprene and ethylene glycol dimethyl ether before reaction at0 hour of commencement of polymerization reaction” and a “relative arearatio of unreacted isoprene and ethylene glycol dimethyl ether afterreaction” according to the following formula 4.

<Measurement Condition of Gas Chromatography>

Apparatus: “GC-14B”, manufactured by Shimadzu Corporation

Column: “Rxi-5 ms” (inside diameter: 0.25 mm, length: 30 m, filmthickness: 0.25 μm), manufactured by Restek Corporation

Carrier gas: Helium (140.0 kPaG) was allowed to flow at a flow rate of1.50 mL/min.

Injection amount of sample: 0.1 μL of the liquid medicine was injectedat a split ratio of 50/1.

Detector: FID

Temperature of detector: 280° C.

Temperature of vaporization chamber: 280° C.

Temperature rise condition: After holding at 40° C. for 10 minutes, thetemperature was raised to 250° C. at a rate of 20° C./min, followed byholding for 5 minutes.

$\begin{matrix}{{{Conversion}\mspace{14mu}(\%)} = {\left( {1 - \frac{\begin{matrix}{{Relative}\mspace{14mu}{area}\mspace{14mu}{ratio}\mspace{14mu}{of}\mspace{14mu} 1,3,7\text{-}{octatriene}} \\{{after}\mspace{14mu}{completion}\mspace{14mu}{of}} \\{{polyermerization}\mspace{14mu}{reaction}}\end{matrix}}{\begin{matrix}{{Relative}\mspace{14mu}{area}\mspace{14mu}{ratio}\mspace{14mu}{of}\mspace{14mu} 1,3,7\text{-}{octatriene}} \\{{at}\mspace{14mu} 0\mspace{14mu}{hour}\mspace{14mu}{of}\mspace{11mu}{commencement}} \\{\;{{of}\mspace{14mu}{polyermerization}\mspace{14mu}{reaction}}}\end{matrix}}} \right) \times 100}} & {\left( {{Formula}\mspace{14mu} 3} \right)\;} \\{{{Conversion}\mspace{14mu}(\%)} = {\left( {1 - \frac{\begin{matrix}{{{Relative}\mspace{14mu}{area}\mspace{14mu}{ratio}\mspace{14mu}{of}\mspace{14mu}{isoprene}\mspace{11mu}{after}}\mspace{11mu}} \\{{completion}\mspace{14mu}{of}\mspace{14mu}{polyermerization}\mspace{14mu}{reaction}}\end{matrix}}{\begin{matrix}{{Relative}\mspace{14mu}{area}\mspace{14mu}{ratio}\mspace{14mu}{of}\mspace{14mu}{isoprene}} \\{{at}\mspace{14mu} 0\mspace{14mu}{hour}\mspace{14mu}{of}\mspace{11mu}{commencement}} \\{{of}\mspace{14mu}{polyermerization}\mspace{14mu}{reaction}}\end{matrix}}} \right) \times 100}} & \left( {{Formula}\mspace{14mu} 4} \right)\end{matrix}$(Measurement Method of Yield of Copolymer)

The yield of the obtained copolymer was determined on a basis of thecharged amount of the raw material monomers according to the followingformula 5.

$\begin{matrix}{{{Yield}\mspace{14mu}(\%)} = {\frac{{Mass}\mspace{14mu}{of}\mspace{14mu}{obtained}\mspace{14mu}{copolymer}\mspace{14mu}(g)}{\begin{matrix}{{{Mass}\mspace{14mu}{of}\mspace{14mu}{raw}\mspace{14mu}{material}\mspace{14mu}{monomers}}\;} \\{{used}\mspace{14mu}{for}\mspace{14mu}{polyermerization}\mspace{14mu}{reaction}\mspace{14mu}(g)}\end{matrix}} \times 100}} & \left( {{Formula}\mspace{14mu} 5} \right)\end{matrix}$(Measurement Method of Weight Average Molecular Weight (Mw) andMolecular Weight Distribution (Mw/Mn))

To 0.10 g of the obtained copolymer, 60.0 g of tetrahydrofuran was addedto prepare a uniform solution; this solution was analyzed by means ofgel permeation chromatography under the following measurement condition,to determine the weight average molecular weight (Mw) and the numberaverage molecular weight (Mn) as expressed in terms of standardpolystyrene; and the molecular weight distribution (Mw/Mn) wascalculated.

<Measurement Condition of Gel Permeation Chromatography>

Apparatus: “HLC-8320GPC EcoSEC”, manufactured by Tosoh Corporation

Column; Two of “TSKgel SuperMultipore HZ-M” (inside diameter: 4.6 mm,length: 150 mm), manufactured by Tosoh Corporation were connected inseries and used.

Eluent: Tetrahydrofuran was allowed to flow at a flow rate of 0.35mL/min.

Injection amount of sample: 10 μL

Detector: RI

Temperature of detector: 40° C.

(Binding Mode)

To 150 mg of the obtained copolymer, 1.00 g of deuterochloroform wasadded to prepare a uniform solution, and this solution was subjected to¹³C-NMR measurement under the following measurement condition.

<¹³C-NMR Measurement Condition>

Apparatus: “JNM-LA500”, manufactured by JEOL Ltd.

Reference material: Tetramethylsilane

Measurement temperature: 25° C.

Cumulative number: 15,000 times

As a result of the ¹³C-NMR measurement, a “peak capable of beingassigned to one carbon atom of the 1,2-bond” of 1,3,7-octatriene wasobserved at δ138.1 to 138.6 ppm; “peaks capable of being assigned to onecarbon atom of the 1,4-bond and one carbon atom of the 3,4-bond” wereobserved at δ138.8 to 139.4 ppm; and a “peak capable of being assignedto one carbon atom of the 3,4-bond” was observed at 6140.9 to 141.6 ppm.A value obtained by subtracting a peak area at 6140.9 to 141.6 ppm froma peak area at 6138.8 to 139.4 ppm was defined as a peak areacorresponding to one carbon atom of the 1,4-bond.

A “peak capable of being assigned to one carbon atom of the 1,2-bond” ofisoprene was observed at δ140.5 to 141.0 ppm; a “peak capable of beingassigned to one carbon atom of the 1,4-bond” was observed at δ122.0 to126.9 ppm; and a “peak capable of being assigned to one carbon atom ofthe 3,4-bond” was observed at δ110.2 to 112.2 ppm.

A ratio of each of the 1,2-bond, the 1,4-bond, and the 3,4-bond derivedfrom 1,3,7-octatriene and a ratio of each of the 1,2-bond, the 1,4-bond,and the 3,4-bond derived from isoprene, each of which was contained inthe copolymer, were determined according to the following formulae 6 to8, respectively.

$\begin{matrix}{{{Ratio}\mspace{14mu}{of}\mspace{14mu}{the}\mspace{14mu} 1,2\text{-}{bond}\mspace{14mu}(\%)} = \frac{{Peak}\mspace{14mu}{area}\mspace{14mu}{assigned}\mspace{14mu}{to}\mspace{14mu}{the}\mspace{14mu} 1,2\text{-}{bond}}{\begin{matrix}{{Sum}\mspace{14mu}{total}\mspace{14mu}{of}\mspace{14mu}{peak}\mspace{14mu}{areas}\mspace{14mu}{assigned}\mspace{14mu}{to}\mspace{14mu}{the}} \\{{1,2\text{-}{bond}},{{the}\mspace{14mu} 1,4\text{-}{bond}},{{and}\mspace{14mu}{the}\mspace{14mu} 3,4\text{-}{bond}}}\end{matrix}}} & \left( {{Formula}\mspace{14mu} 6} \right) \\{{{Ratio}\mspace{14mu}{of}\mspace{14mu}{the}\mspace{14mu} 1,4\text{-}{bond}\mspace{14mu}(\%)} = \frac{{Peak}\mspace{14mu}{area}\mspace{14mu}{assigned}\mspace{14mu}{to}\mspace{14mu}{the}\mspace{14mu} 1,4\text{-}{bond}}{\begin{matrix}{{Sum}\mspace{14mu}{total}\mspace{14mu}{of}\mspace{14mu}{peak}\mspace{14mu}{areas}\mspace{14mu}{assigned}\mspace{14mu}{to}\mspace{14mu}{the}} \\{{1,2\text{-}{bond}},{{the}\mspace{14mu} 1,4\text{-}{bond}},{{and}\mspace{14mu}{the}\mspace{14mu} 3,4\text{-}{bond}}}\end{matrix}}} & \left( {{Formula}\mspace{14mu} 7} \right) \\{{{Ratio}\mspace{14mu}{of}\mspace{14mu}{the}\mspace{14mu} 3,4\text{-}{bond}\mspace{14mu}(\%)} = \frac{{Peak}\mspace{14mu}{area}\mspace{14mu}{assigned}\mspace{14mu}{to}\mspace{14mu}{the}\mspace{14mu} 3,4\text{-}{bond}}{\begin{matrix}{{Sum}\mspace{14mu}{total}\mspace{14mu}{of}\mspace{14mu}{peak}\mspace{14mu}{areas}\mspace{14mu}{assigned}\mspace{14mu}{to}\mspace{14mu}{the}} \\{{1,2\text{-}{bond}},{{the}\mspace{14mu} 1,4\text{-}{bond}},{{and}\mspace{14mu}{the}\mspace{14mu} 3,4\text{-}{bond}}}\end{matrix}}} & \left( {{Formula}\mspace{14mu} 8} \right)\end{matrix}$

Example 1 Production of Copolymer

The interior of an SUS316 (registered trademark)-made autoclave having acapacity of 1 L and equipped with a thermometer, an electric heater, anelectromagnetic induction agitator, a chemical liquid charging port, anda sampling port was purged with argon, and then, 232.0 g of cyclohexanewas charged. Subsequently, the internal pressure was regulated withargon to 0.1 MPaG, and then, the temperature was raised to 50° C. over30 minutes while stirring at 250 rpm. 0.278 g (3.85 mmol) oftetrahydrofuran (THF) was charged in an argon gas stream, subsequently,0.611 g of a cyclohexane solution containing 1.260 mmol/g ofsec-butyllithium (0.77 mmol in terms of sec-butyllithium) was charged,and then, the internal pressure was regulated with argon to 0.3 MPaG.

Meanwhile, 86.22 g (0.797 mol) of 1,3,7-octatriene obtained inProduction Example 1 and 69.07 g (1.014 mol) of isoprene were mixed, andthen, the mixture was fed into the autoclave having sec-butyllithiumresided therein over 1 hour. The point of time when the charging wascommenced was defined as 0 hour of commencement of the polymerizationreaction, and the reaction was performed for 6.5 hours while controllingthe liquid temperature to 50° C.

Thereafter, 0.32 g of a cyclohexane solution containing 2.50 mmol/g ofethanol (0.80 mmol in terms of ethanol) was added, thereby terminatingthe polymerization reaction.

Subsequently, the whole amount of the obtained polymerization-terminatedliquid was transferred into a 1-L eggplant type flask, and almost of allof the solvent was distilled off while heating at 40° C. and at 100 kPaAby using a rotatory evaporator. Furthermore, the aforementioned eggplanttype flask was transferred into a vacuum dryer and dried for 12 hourswhile heating at 25° C. and at 0.1 kPaA, thereby acquiring 153.1 g of acopolymer in a liquid state. The use amount of each of the reagents, thereaction condition, and the reaction results are shown in Table 2.

Examples 2 to 14

Copolymers were obtained by performing the polymerization reaction inthe same manner as in Example 1, except that each of the reagents andthe use amount thereof and the reaction condition were changed to thoseas shown in Table 2. The polymerization time was one described in Table2. The use amount of each of the reagents, the reaction condition, andthe reaction results are shown in Table 2.

Examples 15 and 16

Copolymers were obtained by performing the polymerization reaction inthe same manner as in Example 1, except for using the 1,3,7-octatrieneobtained in Production Example 2 in places of the 1,3,7-octatrieneobtained in Production Example 1 and further changing each of thereagents and the use amount thereof and the reaction condition as shownin Table 3. The polymerization time was one described in Table 3. Theuse amount of each of the reagents, the reaction condition, and thereaction results are shown in Table 3.

Example 17

A copolymer was obtained by performing the polymerization reaction inthe same manner as in Example 1, except for using the 1,3,7-octatrieneobtained in Production Example 3 in places of the 1,3,7-octatrieneobtained in Production Example 1 and further changing each of thereagents and the use amount thereof and the reaction condition as shownin Table 3. The polymerization time was one described in Table 3. Theuse amount of each of the reagents, the reaction condition, and thereaction results are shown in Table 3.

Example 18

A copolymer was obtained by performing the polymerization reaction inthe same manner as in Example 2, except for changing the use amount oftetrahydrofuran (THF) from 0.689 g (9.55 mmol) to 27.542 g (382 mmol).The polymerization time was one described in Table 3. The use amount ofeach of the reagents, the reaction condition, and the reaction resultsare shown in Table 3.

Example 19

A copolymer was obtained by performing the polymerization reaction inthe same manner as in Example 12, except for changing the use amount ofN,N,N′,N′-tetramethylethylenediamine (TMEDA) from 0.182 g (1.57 mmol) to0.728 g (6.26 mmol). The polymerization time was one described in Table3. The use amount of each of the reagents, the reaction condition, andthe reaction results are shown in Table 3.

Examples 20 and 21

Copolymers were obtained by performing the polymerization reaction inthe same manner as in Example 2, except for changing the polymerizationtemperature and the polymerization time as shown in Table 3. Thepolymerization time was one described in Table 3. The use amount of eachof the reagents, the reaction condition, and the reaction results areshown in Table 3.

Examples 22 and 23

Copolymers were obtained by performing the polymerization reaction inthe same manner as in Example 1, except that the use amount of each ofreagents was changed to one as shown in Table 3, thereby regulating asolid content concentration of the reaction liquid after completion ofthe anionic polymerization to 20% by mass and 61% by mass, respectively.The polymerization time was 1 hour and 2 hours, respectively. The useamount of each of the reagents, the reaction condition, and the reactionresults are shown in Table 3.

Example 24(1)

A copolymer having a living anionic active species at a molecular endthereof was obtained by performing the reaction for 5 hours in the samemanner as in Example 1, except that the use amount of each of reagentswas changed to one as shown in Table 3, thereby regulating a solidcontent concentration of the reaction liquid after completion of theanionic polymerization to 30% by mass. The use amount of each of thereagents, the reaction condition, and the reaction results are shown inTable 3.

Example 24(2)

To the autoclave containing the copolymer having a living anionic activespecies at a molecular end thereof as obtained in Example 24(1), 52.45 g(0.485 mol) of the 1,3,7-octatriene obtained in Production Example 1 and41.99 g (0.616 mol) of isoprene were added, and the contents wereallowed to react with each other for 6 hours, thereby obtaining acopolymer. The use amount of each of the reagents, the reactioncondition, and the reaction results are shown in Table 3.

Comparative Example 1

A copolymer was obtained by performing the polymerization reaction inthe same manner as in Example 17, except that the 1,3,7-octatrieneobtained in Production Example 4 was used in place of the1,3,7-octatriene obtained in Production Example 1. The polymerizationtime was one described in Table 3. The use amount of each of thereagents, the reaction condition, and the reaction results are shown inTable 3.

Reference Example 1

A copolymer was obtained by performing the polymerization reaction inthe same manner as in Example 17, except that the 1,3,7-octatrieneobtained in Production Example 5 was used in place of the1,3,7-octatriene obtained in Production Example 1. The polymerizationtime was one described in Table 3. The use amount of each of thereagents, the reaction condition, and the reaction results are shown inTable 3.

Reference Example 2

A copolymer was obtained by performing the polymerization reaction inthe same manner as in Example 17, except that the 1,3,7-octatrieneobtained in Production Example 6 was used in place of the1,3,7-octatriene obtained in Production Example 1. The polymerizationtime was one described in Table 3. The use amount of each of thereagents, the reaction condition, and the reaction results are shown inTable 3.

TABLE 2 Example 1 2 3 4 5 6 7 Reaction condition Purity of1,3,7-octatriene (%) 99.3 99.3 99.3 99.3 99.3 99.3 99.3 Total content ofperoxide and its <0.015 <0.015 <0.015 <0.015 <0.015 <0.015 <0.015decomposition product (mmol/kg) Use amount of 1,3,7-octatriene (mol)0.797 0.797 0.797 1.389 1.389 1.389 0.113 Use amount of isoprene (mol)1.014 1.014 1.014 0.0716 0.0716 0.0716 2.101 Total use amount of rawmaterial monomers 1.811 1.811 1.811 1.4606 1.4606 1.4606 2.214 (mol)Content α of 1,3,7-octatriene (mol %) 44.01 44.01 44.01 95.10 95.1095.10 5.10 Use amount of 1,3,7-octatriene (g) 86.22 86.22 86.22 150.26150.26 150.26 12.22 Use amount of isoprene (g) 69.07 69.07 69.07 4.884.88 4.88 143.12 Use amount of cyclohexane (g) 232.0 232.0 210.2 232.0232.0 224.8 232.0 Solid content concentration after completion 40 40 4040 40 40 40 of polymerization reaction (mass %) Use amount of anionicpolymerization initiator 0.77 1.91 19.74 1.34 2.81 6.83 1.00 (mmol)(Total amount of raw material monomers)/ 2352 948 92 1090 520 214 2214(Anionic polymerization initiator) (molar ratio) Kind of Lewis base THFTHF THF THF THF THF THF Use amount of Lewis base (g) 0.278 0.689 7.1170.483 1.013 2.463 0.361 Use amount of Lewis base (mmol) 3.85 9.55 98.706.70 14.05 34.15 5.00 (Lewis base)/(Anionic polymerization initiator) 55 5 5 5 5 5 (molar ratio) Polymerization temperature (° C.) 50 50 50 5050 50 50 Polymerization time (hr) 6.5 4 2.5 5 2 0.5 6 Reaction resultsConversion of 1,3,7-octatriene (%) 96.6 97.9 99.0 99.1 99.1 99.3 95.2Conversion of isoprene (%) >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9Weight average molecular weight (Mw) of 298,890 132,040 21,990 171,54095,610 51,710 297,060 copolymer Molecular weight distribution (Mw/Mn) of1.78 1.32 1.21 1.65 1.32 1.21 1.10 copolymer Numerical value determinedaccording to the 2.14 1.61 1.26 1.74 1.50 1.36 2.13 formula (i) Rate of1,2-bond of octatriene (%) 44.5 44.8 49.4 48.2 — — 41.8 Rate of 1,4-bondof octatriene (%) 55.5 55.2 48.0 48.8 — — 58.2 Rate of 3,4-bond ofoctatriene (%) Undetected Undetected 2.6 3.1 — — Undetected Rate of1,2-bond of isoprene (%) Undetected Undetected 2.2 Undetected — —Undetected Rate of 1,4-bond of isoprene (%) 71.6 59.1 29.7 56.0 — — 71.4Rate of 3.4-bond of isoprene (%) 28.4 40.9 68.1 44.0 — — 28.6 Example 89 10 11 12 13 14 Reaction condition Purity of 1,3,7-octatriene (%) 99.399.3 99.3 99.3 99.3 99.3 99.3 Total content of peroxide and its <0.015<0.015 <0.015 <0.015 <0.015 <0.015 <0.015 decomposition product(mmol/kg) Use amount of 1,3,7-octatriene (mol) 0.113 0.113 1.389 1.3891.389 1.389 1.389 Use amount of isoprene (mol) 2.101 2.101 0.0716 0.07160.0716 0.0716 0.0716 Total use amount of raw material monomers 2.2142.214 1.4606 1.4606 1.4606 1.4606 1.4606 (mol) Content α of1,3,7-octatriene (mol %) 5.10 5.10 95.10 95.10 95.10 95.10 95.10 Useamount of 1,3,7-octatriene (g) 12.22 12.22 150.26 150.26 150.26 150.26150.26 Use amount of isoprene (g) 143.12 143.12 4.88 4.88 4.88 4.88 4.88Use amount of cyclohexane (g) 232.0 232.0 232.0 232.0 232.0 232.0 232.0Solid content concentration after completion 40 40 40 40 40 40 40 ofpolymerization reaction (mass %) Use amount of anionic polymerizationinitiator 2.69 4.96 3.13 3.13 3.13 3.13 3.13 (mmol) (Total amount of rawmaterial monomers)/ 823 446 467 467 467 467 467 (Anionic polymerizationinitiator) (molar ratio) Kind of Lewis base THF THF Et₂O NEt₃ TMEDA DEEDTHFP Use amount of Lewis base (g) 0.970 1.788 1.160 1.584 0.182 0.1740.260 Use amount of Lewis base (mmol) 13.45 24.80 15.65 15.65 1.57 1.471.41 (Lewis base)/(Anionic polymerization initiator) 5 5 5 5 0.5 0.470.45 (molar ratio) Polymerization temperature (° C.) 50 50 50 50 50 5050 Polymerization time (hr) 2 1 7 6 5 4 6 Reaction results Conversion of1,3,7-octatriene (%) 98.5 99.7 99.3 99.2 99.4 98.8 99.2 Conversion ofisoprene (%) >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 Weight averagemolecular weight (Mw) of 105,430 45,360 75,340 72,080 88,020 73,55078,660 copolymer Molecular weight distribution (Mw/Mn) of 1.09 1.05 1.331.34 1.49 1.39 1.43 copolymer Numerical value determined according tothe 1.53 1.34 1.43 1.42 1.47 1.43 1.44 formula (i) Rate of 1,2-bond ofoctatriene (%) — 47.3 — — 47.9 — — Rate of 1,4-bond of octatriene (%) —52.7 — — 44.8 — — Rate of 3,4-bond of octatriene (%) — Undetected — —7.3 — — Rate of 1,2-bond of isoprene (%) — Undetected — — 7.5 — — Rateof 1,4-bond of isoprene (%) — 45.0 — — 69.0 — — Rate of 3.4-bond ofisoprene (%) — 55.0 — — 23.5 — —

TABLE 3 Example 15 16 17 18 19 20 21 Reaction condition Purity of1,3,7-octatriene (%) 99.2 99.2 99.2 99.3 99.3 99.3 99.3 Total content ofperoxide and its 0.065 0.065 0.26 <0.015 <0.015 <0.015 <0.015decomposition product (mmol/kg) Use amount of 1,3,7-octatriene (mol)0.797 1.389 1.389 0.797 1.389 0.797 0.797 Use amount of isoprene (mol)1.014 0.0716 0.0716 1.014 0.0716 1.014 1.014 Total use amount of rawmaterial 1.811 1.4606 1.4606 1.811 1.4606 1.811 1.811 monomers (mol)Content α of 1,3,7-octatriene 44.01 95.10 95.10 44.01 95.10 44.01 44.01(mol %) Use amount of 1,3,7-octatriene (g) 86.22 150.26 150.26 86.22150.26 86.22 86.22 Use amount of isoprene (g) 69.07 4.88 4.88 69.07 4.8869.07 69.07 Use amount of cyclohexane (g) 232.0 232.0 232.0 203.9 232.0232.0 232.0 Solid content concentration after 40 40 40 40 40 40 40completion of polymerization reaction (mass %) Use amount of anionicpolymerization 1.91 3.00 3.00 1.91 3.13 1.91 1.91 initiator (mmol)(Total amount of raw material monomers)/ 948 487 487 948 467 948 948(Anionic polymerization initiator) (molar ratio) Kind of Lewis base — —TMEDA THF TMEDA THF THF Use amount of Lewis base (g) — — 0.349 27.5420.728 0.689 0.689 Use amount of Lewis base (mmol) — — 3.00 382.00 6.269.55 9.55 (Lewis base)/(Anionic polymerization — — 1 200 2 5 5initiator) (molar ratio) Polymerization temperature (° C.) 50 50 50 5050 30 85 Polymerization time (hr) 8 8 10 7 8 12 1 Reaction time afteraddition of 1,3,7- octatriene and isoprene (hr) Reaction resultsConversion of 1,3,7-octatriene (%) 81.4 82.3 90.3 82.9 88.8 98.2 99.8Conversion of isoprene (%) >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9Weight average molecular weight (Mw) 100,730 50,490 54,970 122,79067,100 107,890 178,770 of copolymer Molecular weight distribution(Mw/Mn) 1.08 1.18 1.25 1.87 1.67 1.24 1.76 of copolymer Numerical valuedetermined according 1.51 1.35 1.37 1.58 1.41 1.54 1.76 to the formula(i) Rate of 1,2-bond of octatriene (%) 45.9 — — 46.5 — 44.3 47.4 Rate of1,4-bond of octatriene (%) 53.4 — — 49.0 — 54.7 50.7 Rate of 3,4-bond ofoctatriene (%) 0.7 — — 4.5 — 1.0 1.9 Rate of 1,2-bond of isoprene (%)0.0 — — 1.8 — 2.0 0.6 Rate of 1,4-bond of isoprene (%) 93.2 — — 13.5 —40.0 62.6 Rate of 3.4-bond of isoprene (%) 6.8 — — 84.7 — 58.0 36.8Comparative Example Example Reference Example 22 23 24(1) 24(2) 1 1 2Reaction condition Purity of 1,3,7-octatriene (%) 99.3 99.3 99.3 99.397.98 96.72 99.2 Total content of peroxide and its <0.015 <0.015 <0.015<0.015 0.062 0.073 3.37 decomposition product (mmol/kg) Use amount of1,3,7-octatriene (mol) 0.517 1.64 0.512 0.997 1.389 1.389 1.389 Useamount of isoprene (mol) 0.316 1.003 0.652 1.268 0.0716 0.0716 0.0716Total use amount of raw material 0.833 2.643 1.164 2.265 1.4606 1.46061.4606 monomers (mol) Content α of 1,3,7-octatriene 62.04 62.04 44.0144.01 95.10 95.10 95.10 (mol %) Use amount of 1,3,7-octatriene (g) 55.89177.42 55.41 107.86 150.26 150.26 150.26 Use amount of isoprene (g)21.53 68.34 44.39 86.38 4.88 4.88 4.88 Use amount of cyclohexane (g)310.0 146.0 232.0 232.0 232.0 232.0 232.0 Solid content concentrationafter 20 61 30 45 40 40 40 completion of polymerization reaction (mass%) Use amount of anionic polymerization 4.45 14.00 2.39 2.39 3.00 3.003.00 initiator (mmol) (Total amount of raw material monomers)/ 187 189487 948 487 487 487 (Anionic polymerization initiator) (molar ratio)Kind of Lewis base THF THF THF THF TMEDA TMEDA TMEDA Use amount of Lewisbase (g) 1.604 0.068 0.862 0.862 0.349 0.349 0.349 Use amount of Lewisbase (mmol) 22.25 0.94 11.95 11.95 3.00 3.00 3.00 (Lewis base)/(Anionicpolymerization 5 5 5 5 1 1 1 initiator) (molar ratio) Polymerizationtemperature (° C.) 50 50 50 50 50 50 50 Polymerization time (hr) 1 2 5 88 3 Reaction time after addition of 1,3,7- 6 octatriene and isoprene(hr) Reaction results Conversion of 1,3,7-octatriene (%) 98.6 >99.9 99.098.2 94.8 84.6 24.9 Conversion of isoprene(%) >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 >99.9 Weight average molecularweight (Mw) 23,760 39,530 67,700 152,200 57,220 55,100 30,330 ofcopolymer Molecular weight distribution (Mw/Mn) 1.12 1.24 1.30 1.50 2.072.03 1.99 of copolymer Numerical value determined according 1.27 1.321.41 1.67 1.38 1.37 1.29 to the formula (i) Rate of 1,2-bond ofoctatriene (%) 49.3 47.4 45 44.8 — — — Rate of 1,4-bond of octatriene(%) 48.4 49.7 55 55.2 — — — Rate of 3,4-bond of octatriene (%) 2.3 2.9Undetected Undetected — — — Rate of 1,2-bond of isoprene (%) 1.2 2.5Undetected Undetected — — — Rate of 1,4-bond of isoprene (%) 39.2 26.647 53.0 — — — Rate of 3.4-bond of isoprene (%) 59.6 70.9 53 47.0 — — —

The Lewis bases described in Tables 2 and 3 are as follows.

THF: Tetrahydrofuran

Et₂O: Diethyl ether

NEt₃: Triethylamine

TMEDA: N,N,N′,N′-Tetramethylethylenediamine

DEE: 1,2-Diethoxyethane

DTHFP: 2,2-Di(2-tetrahydrofuryl)propane

From Tables 2 and 3, the copolymers obtained by subjecting1,3,7-octatriene having not only a purity of more than 98.0% but also atotal content of a peroxide and its decomposition product of 0.30mmol/kg or less and isoprene to anionic polymerization (see theExamples) are narrower in the molecular weight distribution (Mw/Mn) thanthe copolymers obtained by subjecting 1,3,7-octatriene having a purityof 98.0% or less or having a total content of a peroxide and itsdecomposition product of more than 0.30 mmol/kg and isoprene to anionicpolymerization (see the Comparative Example or Reference Examples). Inthis way, nevertheless a difference in each of the purity and the totalcontent of a peroxide and its decomposition product was not large, asfor the copolymers obtained in the Examples, the molecular weightdistribution (Mw/Mn) could be made narrow. In addition, in the Examples,there is a tendency that a high conversion can be achieved for a shorttime, as compared with the Comparative Example or Reference Examples.Furthermore, as for the copolymers obtained in the Examples, thosehaving a large weight average molecular weight (Mw) can be obtained,too.

With respect to the copolymers obtained in Examples 2, 3, 5 to 11, 13 to17, 20, 22, and 23, the molecular weight distribution (Mw/Mn) is lessthan 1.44.

The copolymers obtained in Examples 1 to 11, 13 to 17, 20, 22, 23,24(1), and 24(2) are a copolymer having a molecular weight distribution(Mw/Mn) smaller than the value determined according the formula (i).

The copolymers obtained in Examples 1 to 6, 10 to 23, 24(1), and 24(2)are a copolymer in which not only the content of the structural unitderived from 1,3,7-octatriene is more than 21.0 mol % relative to thetotal amount of the structural unit derived from 1,3,7-octatriene andthe structural unit derived from isoprene, but also the molecular weightdistribution (Mw/Mn) is less than 2.06.

In addition, from the results of Examples 1 to 14, 17 to 23, 24(1), and24(2) using the Lewis base and the results of Example 15 to 16 not usingthe Lewis base, it is noted that in the case of using the Lewis base,there is a tendency that the high conversion can be achieved, and inparticular, it is easy to achieve the high conversion for a short time.

Furthermore, as demonstrated in Examples 22 and 23, even by performingthe polymerization reaction by regulating the solid contentconcentration after completion of the anionic polymerization to 20% bymass or 61% by mass, the copolymers of 1,3,7-octatriene having a narrowmolecular weight distribution (Mw/Mn) could be obtained.

Example 25 Production of Hydride

(Production of Copolymer as Precursor of Hydrogenated Polymer)

The same operations as in Example 1 were followed to acquire acyclohexane solution containing a copolymer formed from 1,3,7-octatrieneand isoprene.

(Preparation of Hydrogenation Catalyst)

In a 1-L three-necked flask having been purged with nitrogen, 25.1 g ofa 2-ethylhexanoic acid solution of nickel(II) bis(2-ethylhexanoate)(containing 53.5 mmol of a nickel atom) (manufactured by Wako PureChemical Industries, Ltd.) was dissolved in 284.4 g of cyclohexane, 31.8g (160.3 mmol) of triisobutylaluminum (manufactured by Nippon AluminumAlkyls, Ltd.) was then added over 10 minutes, and the contents werestirred for 30 minutes, to prepare a hydrogenation catalyst. Thishydrogenation catalyst was used for the following hydrogenationreaction.

(Hydrogenation Reaction)

The autoclave in which the aforementioned copolymer had been producedwas cooled to 25° C., 290 g of the polymer solution was then extracted,and subsequently, 290 g of cyclohexane was introduced. The interior ofthe autoclave was purged with a hydrogen gas and further pressurizedwith a hydrogen gas to 0.2 MPaG, and subsequently, the autoclave washeated such that the liquid temperature reached 75° C. Thereafter, 0.49g of the aforementioned hydrogenation catalyst (corresponding to 114.55ppm by mass in terms of a nickel metal relative to the copolymer) wasadded, and subsequently, the contents were allowed to react for 2 hoursby regulating the internal pressure with a hydrogen gas to 0.98 MPaG.

Thereafter, 0.49 g of the aforementioned hydrogenation catalyst(corresponding to 114.55 ppm by mass in terms of a nickel metal relativeto the copolymer) was added three times at intervals of 2 hours. The useamount of the hydrogenation catalyst was 458.2 ppm by mass in total asexpressed in terms of a nickel metal relative to the copolymer, and thetime of the hydrogenation reaction was 8 hours after first introductionof the hydrogenation catalyst.

First of all, to 150 mg of the copolymer before hydrogenation, 10 mg ofstandard polystyrene was added, and then, 1.00 g of deuterochloroformwas added, thereby preparing a uniform solution. This solution wassubjected to ¹H-NMR measurement under the following measurementcondition. In addition, to 150 mg of the hydride of the copolymer, 10 mgof standard polystyrene was added, and then, 1.00 g of deuterochloroformwas added, thereby preparing a uniform solution. This solution was alsosubjected to ¹H-NMR measurement under the following measurementcondition.

As a result of the ¹H-NMR measurement under the following condition, asthe binding modes constituted of octatrienes as a structural unit,“peaks capable of being assigned to four hydrogen atoms of the 1,2-bond,four hydrogen atoms of the 1,4-bond, and four hydrogen atoms of the3,4-bond” were observed at δ4.8 to 5.5 ppm; a “peak capable of beingassigned to one hydrogen atom of the 3,4-bond” was observed at δ5.5 to5.7 ppm; and “peaks capable of being assigned to one hydrogen atom ofthe 1,2-bond, one hydrogen atom of the 1,4-bond, and one hydrogen atomof the 3,4-bond” were observed at δ5.7 to 5.9 ppm. As the binding modesconstituted of isoprene as a structural unit, “peaks capable of beingassigned to two hydrogen atoms of the 3,4-bond” were observed at δ4.6 to4.8 ppm; a “peak capable of being assigned to one hydrogen atom of the1,4-bond” was observed at δ5.1 to 5.3 ppm; and a “peak capable of beingassigned to one hydrogen atom of the 1,2-bond” was observed at δ5.7 to6.0 ppm. In addition, “peaks capable of being assigned to five hydrogenatoms of the aromatic ring of polystyrene” were observed at δ6.2 to 7.5ppm.

From the molar number of the double bonds of non-hydrogenated1,3,7-octatriene and isoprene relative to the total molar number ofstyrene in the copolymer before the hydrogenation and the molar numberof the double bonds of non-hydrogenated 1,3,7-octatriene and isoprenerelative to the total molar number of styrene in the copolymer after thehydrogenation treatment, a hydrogenation rate as a ratio of the materialhydrogenated with the double bonds derived from 1,3,7-octatriene andisoprene was calculated to be 98.6%.

<¹H-NMR Measurement Condition>

Apparatus: “JNM-LA500”, manufactured by JEOL Ltd.

Reference material: Tetramethylsilane

Measurement temperature: 25° C.

Cumulative number: 254 times

INDUSTRIAL APPLICABILITY

The copolymer of the present invention is useful as a raw material ofadhesives and lubricating agents as well as a functional material suchas a lubricant for various rubbers and a modifier.

The invention claimed is:
 1. A copolymer comprising a structural unitderived from 1,3,7-octatriene and a structural unit derived fromisoprene, the copolymer having a molecular weight distribution (Mw/Mn)of less than 1.44.
 2. A copolymer comprising a structural unit derivedfrom 1,3,7-octatriene and a structural unit derived from isoprene, thecopolymer having a molecular weight distribution (Mw/Mn) smaller than avalue determined according to the following formula (i):3.1569×10⁻⁶×[Weight average molecular weight (Mw)]+1.1945   (i).
 3. Acopolymer comprising a structural unit derived from 1,3,7-octatriene anda structural unit derived from isoprene, wherein a content of thestructural unit derived from 1,3,7-octatriene is more than 21.0 mol %relative to a total amount of the structural unit derived from1,3,7-octatriene and the structural unit derived from isoprene, andwherein a molecular weight distribution (Mw/Mn) of the copolymer is lessthan 2.06.
 4. The copolymer according to claim 1, having a weightaverage molecular weight (Mw) of 5,000 to 500,000.
 5. The copolymeraccording to claim 1, having a weight average molecular weight (Mw) of20,000 to 500,000.
 6. The copolymer according to claim 1, having aweight average molecular weight (Mw) of 50,000 to 500,000.
 7. Thecopolymer according to claim 1, having a weight average molecular weight(Mw) of 210,000 to 500,000.
 8. The copolymer according to claim 1, nothaving a living anionic active species at a molecular end thereof. 9.The copolymer according to claim 1, having a living anionic activespecies at a molecular end thereof.
 10. A copolymer comprising astructural unit derived from 1,3,7-octatriene and a structural unitderived from isoprene, the copolymer having a living anionic activespecies at a molecular end thereof and having a molecular weightdistribution (Mw/Mn) of 2.50 or less.
 11. The copolymer according toclaim 10, having a weight average molecular weight (Mw) of 5,000 to500,000.
 12. The copolymer according to claim 1, further comprising astructural unit derived from a conjugated diene compound having 6 ormore carbon atoms.
 13. The copolymer according to claim 12, wherein theconjugated diene compound having 6 or more carbon atoms is at least oneselected from the group consisting of 2,3-dimethyl-1,3-butadiene,4,5-diethyl-1,3-butadiene, 2-phenyl-1,3-butadiene,2-hexyl-1,3-butadiene, 2-benzyl-1,3-butadiene, 2-p-toluyl-1,3-butadiene,2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene,2,3-dimethyl-1,3-pentadiene, 2,3-diethyl-1,3-pentadiene, 1,3-hexadiene,2,3-dimethyl-1,3-hexadiene, 2,3-diethyl-1,3-heptadiene,3-butyl-1,3-octadiene, 2,3-dimethyl-1,3-octadiene,4,5-diethyl-1,3-octadiene, 1,3-cyclohexadiene, and myrcene.
 14. Ahydride of the copolymer according to claim
 1. 15. A method of producinga copolymer containing a structural unit derived from 1,3,7-octatrieneand a structural unit derived from isoprene, the method comprisingsubjecting 1,3,7-octatriene having a purity, as determined by gaschromatography, of more than 98.0% and isoprene to anionicpolymerization, wherein impurities optionally contained in the1,3,7-octatriene include at least one selected from the group consistingof a peroxide and its decomposition product, and when contained a totalcontent of the peroxide and its decomposition product in the1,3,7-octatriene is 0.30 mmol/kg or less; and the copolymer satisfies atleast one of the following conditions I to III: Condition I: a molecularweight distribution (Mw/Mn) is less than 1.44; Condition II: a molecularweight distribution (Mw/Mn) is smaller than a value determined accordingto the following formula (i):3.1569×10⁻⁶×[Weight average molecular weight (Mw)]+1.1945   (i); andCondition III: a content of the structural unit derived from1,3,7-octatriene is more than 21.0 mol % relative to a total amount ofthe structural unit derived from 1,3,7-octatriene and the structuralunit derived from isoprene, and a molecular weight distribution (Mw/Mn)thereof is less than 2.06.
 16. The method of claim 15, wherein the1,3,7-octatriene has a purity, as determined by gas chromatography, of98.5% or more.
 17. The method of claim 15, wherein the anionicpolymerization is carried out in the presence of a Lewis base.
 18. Themethod of claim 17, wherein a molar ratio of the Lewis base to apolymerization initiator used for the anionic polymerization [(Lewisbase)/(polymerization initiator)] is from 0.01 to 1,000.
 19. The methodof claim 17, wherein the Lewis base is a compound having at least oneselected from the group consisting of an ether bond and a tertiary aminogroup in a molecule thereof.
 20. The method of claim 17, wherein theLewis base is a compound having one atom having an unshared electronpair.
 21. The method of claim 17, wherein the Lewis base is a compoundhaving two or more atoms having an unshared electron pair.
 22. Themethod of claim 21, wherein the Lewis base has multidentate properties.23. The method of claim 15, wherein a solid content concentration of areaction liquid obtained after completion of the anionic polymerizationis from 10 to 80% by mass.
 24. The method of claim 15, wherein theanionic polymerization is carried out at −50 to 200° C.
 25. The methodof claim 15, wherein a conversion of the 1,3,7-octatriene aftercompletion of the anionic polymerization, as determined by gaschromatography, is 80.0% or more.
 26. The method of claim 15, wherein aconversion of the 1,3,7-octatriene after completion of the anionicpolymerization, as determined by gas chromatography, is 88.0% or more.